KR20220066347A - Method for transferring an embossing structure to the surface of a coating, and a composite usable as an embossing mold - Google Patents

Abstract

The present invention relates to steps (1), (2-i) and (3-i) or (2-ii) and (3-ii) and also at least step (4) and optionally step (5-i) or (5) according to -ii) an embossing structure is applied to at least a part of the surface of the coating composition (C2a) using a composite (S1C1) comprising a substrate (S1) and an at least partially embossed and at least partially cured coating (C1) A method for transferring, wherein the coating composition (C1a) is a radiation-curable coating composition of a defined composition, and the composite (S1C1) is preferably used as an embossing mold (e2) of an embossing tool (E2) will be.

Description

Method for transferring an embossing structure to the surface of a coating, and a composite usable as an embossing mold

The present invention relates to steps (1), (2-i) and (3-i) or (2-ii) and (3-ii) and also at least step (4) and optionally step (5-i) or (5) according to -ii) an embossing structure is applied to at least a part of the surface of the coating composition (C2a) using a composite (S1C1) comprising a substrate (S1) and an at least partially embossed and at least partially cured coating (C1) A method for transferring, wherein the coating composition (C1a) is a radiation-curable coating composition of a defined composition, and the composite (S1C1) is preferably used as an embossing mold (e2) of an embossing tool (E2) will be.

It is customary these days in many applications in industry to provide a workpiece having a structure on its surface in which structural features are in the micrometer range or even in the nanometer range. Such structures are also referred to as microstructures (structures with features in the micrometer range) or nanostructures (structures with features in the nanometer range). Such structures are used to influence, for example, the visual, bionic and/or tactile qualities of the material surface. Structures of this kind are also referred to as embossments, embossed structures or structured surfaces.

One common method for creating such structured surfaces is to transfer these structures into a coating material. The transfer of the structure to the coating material is frequently accomplished by an embossing operation, in which a mold containing, in inverted form, the microstructures and/or nanostructures to be formed is brought into contact with the coating material and stamped into the coating material. The coating material is typically cured in situ to obtain a permanently formed structure.

WO 90/15673 A1 discloses a method in which a radiation-curable coating material is applied to a film or to an embossed mold having the desired embossing structure in reverse, followed by printing the embossing tool on the foil or on the foil provided with the coating material is described. While the radiation-curable coating material is still positioned between the foil and the embossing tool, curing is performed, followed by removal of the tool to obtain a film provided with the radiation-cured coating material comprising the desired original feature structure. European patent EP 1 135 267 B1 also describes a method of this kind, in which a curable coating material is applied to the surface of a substrate for decoration and a corresponding embossed mold with an inverted pattern is pressed into an uncured coating layer. do. After that, the coating layer is cured and the embossing mold is subsequently removed. EP 3 178 653 A1 discloses an article comprising a flexible fabric having a textured surface for use in replica casting of a curable system. Fabrics can have polymeric layers that can be made using monofunctional and polyfunctional acrylates.

U.S. Pat. No. 9,778,564 B2 discloses an imprinting material comprising a component essentially comprising (meth)acrylamide structural units, and also a further component having 2 to 6 polymerizable groups, a component also having alkylene oxide units. has been disclosed. After application of this material to the substrate, the film obtained therefrom can be provided with a pattern using a nickel embossing tool during its curing by UV radiation.

US 2007/0204953 A1 discloses a method for patterning an adhesive resin, comprising sequentially applying a curable layer of an adhesive resin to a substrate to provide a substrate provided with a cured adhesive resin comprising a desired patterning; , applying a structured pattern to the layer and subsequently curing the layer.

WO 2015/154866 A1 relates to a method for producing a substrate with a structured surface. In this case, first, a first UV-curable coating is applied to the substrate and cured. A second UV-cured coating is then applied over this cured coating as an embossing varnish, which is embossed to create microstructures and subsequently cured.

DE 10 2007 062 123 A1 describes an embossed film by applying an embossing varnish such as, for example, a UV-crosslinkable embossing varnish to a carrier film, structuring the embossing varnish in the micrometer range and curing the embossing varnish applied to the film. A method is described for providing a . However, a disadvantage of such modeling with subsequent metallization is that it results in an undesirable degradation of the modeling quality.

EP 2 146 805 B1 describes a method for producing a material with a textured surface. The method involves providing a curable coating to a substrate, contacting the coating with a texturing medium for embossing, and then curing the embossed coating in this way and removing it from the texturing medium. The texturing medium comprises a surface layer containing 20% to 50% acrylic oligomer, 15% to 35% monofunctional monomer, and 20% to 50% polyfunctional monomer. A similar method is also described in WO 2016/090395 A1 and in ACS Nano Journal, 2016, 10, pages 4926 to 4941, in each case for preparing the surface layer of the texturing medium, a relatively hard It is explicitly taught that a large amount of 3-fold ethoxylated trimethylolpropane triacrylate (TMP(EO) ₃ TA) must be used to be able to create a phosphorous mold. Moreover, according to WO 2016/090395 A1, the coating composition used for preparing the surface layer also contains structural units having at least two thiol groups, such as for example trimethylolpropane tris(3-mercaptopropionate). must be included However, the use of such thiols in the corresponding coating material compositions is often disadvantageous, since such compositions do not always have sufficient stability upon storage and coatings prepared therefrom lack adequate weathering stability. A further factor is the odor problem due to the use of thiols, which is also of course undesirable.

KR 2009/0068490 A contains i) acrylates selected from silicone (meth) acrylates and fluorine (meth) acrylates, ii) certain polyfunctional urethane (meth) acrylates, iii) UV curable monomers, and iv) photoinitiators. It relates to a method for transferring embossed structures of tens of nanometers in micro-patterns using a constructed polymer mold, as well as a method for producing the same for improving the separation of a polymer mold from a substrate without swelling by an organic solvent, wherein the polymer mold is PDMS It has excellent flexibility, mechanical strength and durability compared to a mold made from (polydimethylsiloxane).

Finally, applications WO2019185832A1 and WO2019185833 A1 describe a method for transferring an embossed structure to the surface of a coating composition (B2a) using a composite (F1B1) consisting of a substrate (S1) and an embossed and cured coating (B1) according to specific steps wherein the coating composition (B1a) used for preparing (B1) of the composite (F1B1) is a radiation-curable coating composition of a defined composition, and also an embossing structure on at least a part of the surface of the coating composition (B2a) The use of a composite (F1B1) as an embossing die (p2) of an embossing tool (P2) for transferring is described.

However, the embossing methods known from the prior art, such as those described in particular EP 2 146 805 B1, WO 2016/090395 A1, and in ACS Nano Journal, 2016, 10, pages 4926 to 4941, are especially in the micrometer range. and/or embossments in the nanometer range, ie microstructures and/or nanostructures, cannot always be transferred properly, in particular in the case of such transfers, the accuracy of the molding inevitably deteriorates to an unacceptable degree. At the same time, the embossing is not always properly replicated, or, as in the applications WO2019185832A1 and WO2019185833 A1, the composite used as the embossing mold is allowed to age for a certain time and the embossing mold and the embossed and cured coating are separated immediately after curing. Only when can a high level of replication and non-destructive separation of embossed and cured coatings be obtained.

Accordingly, there is a need for an embossing method that does not have the disadvantages noted above.

It is therefore an object of the present invention to enable coating compositions and methods for transferring embossed structures to a substrate comprising such a coating composition, more particularly to enable the transfer of the corresponding microstructures and/or nanostructures, and to facilitate the transfer of embossed structures. allowing sufficient molding accuracy and a high level of replication success rate even over a larger area of the substrate, so that the embossing is not accompanied by any loss of modulation degree, and also, in particular, of a generally reusable embossing mold for transferring embossing structures. It is to provide a method of this kind that enables the production and/or can be carried out using an embossing mold of this kind. At the same time, the method is particularly prone to embossing due to mismatched surface energies, resulting in loss of unwanted or insufficient properties, such as insufficient adhesion, in particular reduced mold filling and modulation degree, for the coatings and parts of the coating composition used. Replicating the embossing structure to be transferred to a very high level without featuring any disadvantages caused by insufficient adhesion in terms of the repellency of the coating composition to be embossed from the mold by de-wetting of the coating composition. It should be possible, wherein a particularly good separation of the embossing mold and the embossed cured coating should be provided regardless of the time elapsed after the production of the embossing mold and after the embossing mold has come into contact with the coating composition to be embossed. Furthermore, the molding accuracy should be improved over the entire width of the embossing mold.

The above object is solved by the subject matter claimed in the claims and also by preferred embodiments as described below for this subject matter.

Accordingly, a first object of the present invention is a method for transferring an embossing structure to at least a portion of a surface of a coating composition (C2a) using a composite (S1C1), comprising at least steps (1), (2-i) and (3- i) or (2-ii) and (3-ii) and also at least step (4) and optionally step (5-i) or (5-ii), in particular the following steps:

(1) providing a composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1);

and

(2-i) applying at least one coating composition (C2a) to at least a portion of the surface of the substrate (S2) to provide a composite (S2C2a);

(3-i) applying the composite (S1C1) to at least a portion of the coating composition (C2a) of the composite (S2C2a) to provide a composite (S1C1C2aS2);

or

(2-ii) at least one coating composition (C2a) is applied to at least a portion of the at least partially embossed and at least partially cured surface of the composite (S1C1), and the coating composition (C2a) using the composite (S1C1) at least partially embossing to provide a composite (S1C1C2a);

(3-ii) optionally applying the substrate (S2) to at least a portion of the surface formed by the coating composition (C2a) of the composite (S1C1C2a) to provide a composite (S1C1C2aS2);

and

(4) at least partially curing the at least partially embossed coating composition (C2a), optionally applied to the substrate (S2), in contact with the composite (S1C1) throughout the duration of the at least partial cure to make the composite providing (S1C1C2) or (S1C1C2S2);

and

(5-i) optionally, removing the complex (C2S2) in the complex (S1C1C2S2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);

or

(5-ii) optionally, removing the coating (C2) in the complex (S1C1C2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);

wherein the coating is used to prepare the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-i) or step (5-ii) Composition (C1a) is a radiation-curable coating composition comprising:

(a) from 1 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

way.

Surprisingly, the method of the invention is particularly suitable for transferring embossed microstructures and/or nanostructures with a structure width in the range from 10 nm to 1000 μm and a structure depth in the range 1 nm to 1000 μm to the coating composition to be embossed. The time elapsed since the preparation of the composite (S1C1) and the application of the coating composition (C2a) thereto, and the embossing of the coating composition (C2a) applied to this composite (S1C1) advantageously used as an embossing mold and Irrespective of the elapsed time between curing, a very high level of successful replication is possible without loss of good replication quality undergoing less mold filling, and a composite which is preferably used as an embossing mold (e2) of an embossing tool (E2). It has been found that S1C1) has improved layer thickness uniformity across the width of the embossing mold, allowing, if applied, a more uniform application of pressure to the composite S1C1.

Particularly surprisingly in this regard, the process of the invention is obtainable by coating of a radiation-curable coating composition (C1a), preferably on a moving substrate (S1), as an embossing mold (e2) of an embossing tool (E2) It has been found that using the advantageously used composite (S1C1) enables the transfer of the embossed structure with a very high molding accuracy and a high level of replication success over the entire width of the mold.

Further surprisingly, the coating (C1) on the substrate (S1) is characterized by very good adhesion and a very good separation behavior regardless of the elapsed time after aging of the composite (S1C1) and embossing and curing of the coating composition (C2), , it has been found that the method of the invention can be applied very advantageously, since for this reason the corresponding composite (S1C1) can also be used very effectively as an embossing mold (e2).

It is further surprising that the composite (S1C1) usable as an embossing mold (e2) of an embossing tool (E2) in the method of the invention is particularly suitable for transferring embossing structures such as microstructures and/or nanostructures, in particular in the form of continuous embossing molds. It has been found that it can be reused for the purpose of Moreover, surprisingly, such a composite (S1C1), preferably present in the form of a continuous embossing mold (e2), is reusable and therefore not only capable of multiple uses, but also can be inexpensively and quickly produced on a large industrial scale.

Accordingly, a further subject of the invention also consists of a substrate (S1) and a coating (C1) that is at least partially embossed and at least partially cured, applied to at least part of the surface of the substrate (S1) and is at least partially embossed A composite (S1C1) preparable by at least partially curing the engineered coating composition (C1a) by means of radiation curing, comprising:

wherein the coating composition (C1a) is a radiation-curable coating composition comprising:

(a) from 1 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

complex (S1C1).

Preferably this complex (S1C1) is obtainable by carrying out the process steps (6) to (9) described in more detail below.

Surprisingly, the at least partially embossed composite (S1C1) of the present invention can be used as a reusable embossing mold (e2) in an embossing method such as a method of the present invention, preferably as a reusable continuous embossing mold (e2) Furthermore, due to the components present in the radiation-curable coating composition (C1a) used to prepare this composite (S1C1), in particular when carrying out the process of the present invention, its optional steps (5-i) or (5 In -ii), very good separation regardless of the elapsed time after preparation of the composite (S1C1) usable as embossing mold and after application of the coating composition (C2a) or the elapsed time after embossing and curing of this product coating (C2) By quality, it includes such embossed coatings as composites (S1C1) and embossed coatings (C2) and/or corresponding composites such as coatings (C2) which can be used as embossing molds (e2) of the embossing tool (E2). It has been found that it is possible to achieve very effective separation between complexes (S2C2) that are In particular, in the case of carrying out the method steps (6) to (9) for producing the composite (S1C1) in particular, the feature of the embossing mold is formed by complete filling of the mold over the entire width of the mold with a uniform layer thickness. It has been found that the embossed structure of the coating (C1) can be obtained with a high replication success rate and replication quality.

Moreover, a further subject of the invention is an embossing structure, preferably having a microstructured and/or nanostructured surface, in at least part of the surface of the coating composition (C2a), optionally applied to the substrate (S2). Use of the composite (S1C1) of the present invention as an embossing mold (e2) of an embossing tool (E2) for transferring.

When reference is made to an official standard in the context of the present invention, it indicates the version of the standard prevailing at the filing date, or the most recent prevailing version if no version prevailing at the filing date.

In the context of the present invention, for example with reference to a coating composition (C1a) comprising at least one crosslinkable polymer and/or oligomer, the term "at least" is understood to include the specified number (1) and more. should be, for example the coating composition (C1a) will comprise 1, 2, 3 or 4 different or identical crosslinkable polymers and/or oligomers. The mathematical sign relevant to the interpretation of the term "at least" is analogous to "≥". The same applies to the interpretation of the term “at least” in combination with a given numerical range, for example “at least 25% by weight” should be construed in the context of the present invention to mean between 25% and 100% by weight. The term “less than”, such as less than 75% by weight, does not include the recited number (“75”), but should be construed as a range from 0% to 75% by weight. The mathematical sign relevant to the interpretation of the term "less than" is analogous to "<".

In the present specification, for convenience, "polymer" and "resin" are used interchangeably to encompass resins, oligomers and polymers.

The term “poly(meth)acrylate” refers to both polyacrylates and polymethacrylates. Thus, poly(meth)acrylates may consist of acrylates and/or methacrylates and may contain further ethylenically unsaturated monomers such as, for example, styrene or acrylic acid. The term “(meth)acryloyl” in the context of the present invention encompasses methacryloyl compounds, acryloyl compounds and mixtures thereof.

In the context of the present invention, C ₁ -C ₄ -alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl , more preferably methyl and ethyl, most preferably methyl.

In the context of the present invention, in relation to the coating compositions used according to the invention, such as, for example, the coating composition (C1a), and the process of the invention and the process steps thereof, the term "comprising" is preferably " has the definition of "consumed". For example, in connection with the coating composition (C1a) used according to the invention - in addition to components (a) and (b) and also (c) and optionally (d) - the coatings identified below and used according to the invention It is possible that one or more other components optionally present in the composition (C1a) are also included in the composition. All components may each be present in its preferred embodiments identified below. In the context of the process of the present invention, it comprises steps (1), (2-i) and (3-i) or (2-ii) and (3-ii) and also at least step (4) and optionally step (5) In addition to -i) or (5-ii), it may have further optional process steps, such as, for example, steps (6) to (9).

at least step (1), (2-i) and (3-i) or (2-ii) and (3-ii) and also at least step (4) and optionally step (5-i) or (5-ii) ), the method of the present invention for transferring an embossed structure comprising

A first subject of the invention is a method of the invention for transferring an embossed structure to at least a part of the surface of a coating composition (C2a) using a composite (S1C1), as described below, comprising at least steps (1), (2) -i) and (3-i) or (2-ii) and (3-ii) and also at least step (4) and optionally step (5-i) or (5-ii).

The process of the invention is preferably a continuous process.

The embossed structure is transferred or maintained by at least partial embossing of the coating composition (C2a) at least partially applied to the surface of the substrate (S2) according to method steps (2-i) and (3-i). An alternative possibility is transcription by method steps (2-ii) and (3-ii). The term "embossing" refers to at least partially providing the coating composition (C2a), optionally as part of the composite (S2C2a), in at least part of its surface an embossing structure. In this case, at least a predetermined area of the coating composition (C2a) is provided with an embossing structure. Preferably, the entire surface of the coating composition (C2a), optionally as part of the composite (S2C2a), is provided with an embossing structure. Preferably usable as an embossing mold (e2) of an embossing tool (E2), which can be produced according to steps (6) to (9) described below, and a substrate (S1) and at least partially embossed and at least partially cured A similar description applies to the term "embossing" in relation to the at least partially embossed composite (S1C1), consisting of the coating (C1).

Step (1):

In step (1) of the method of the invention, a composite (S1C1) is provided, which consists of a substrate (S1) and an at least partially cured and at least partially embossed coating (C1).

The embossing structures of the composite (S1C1), the embossing mold (e1) and also the composite (S2C2a) and the composite (S2C2) described in the subsequent steps are preferably and in each case independently of one another repeated and/or regularly arranged based on a given pattern or completely random. The structure in each case may be a continuous embossing structure such as a continuous grooved structure or else a plurality of preferably repeating individual embossing structures. In this case each individual embossing structure may ultimately be based on a concave structure having a more or less clearly visible ridge (embossed riser) which preferably defines the embossed height of the embossed structure. Depending on the respective geometry of the ridges of the preferably repeated individual embossing structures, the planarities each differ, for example, preferably sand-shaped, serrated, hexagonal, diamond-shaped, rhombic, parallelogram, honeycomb-shaped. , circular, dotted, star-shaped, rope-shaped, reticulated, polygonal, preferably triangular, square, more preferably rectangular and square, pentagonal, hexagonal, heptagonal and octagonal, wire-shaped, oval, oval and lattice-shaped patterns , it is possible to present a plurality of preferably repeating individual embossing structures, wherein it is also possible for at least two patterns to overlap each other. The ridges of the individual embossing structures may also have a curved, ie convex and/or concave structure.

Preferably, the embossed coating (C1) comprises at least one microstructured and/or nanostructured surface comprising microscale and/or nanoscale surface elements. Each embossed microscale and/or nanoscale surface element can be described by its width such as the width of the ridge, i.e. its structure width, and the height of the embossing, i.e. its structure height (or structure depth). . The structure width, such as the width of the ridge, may have a length of up to 1 centimeter, but is preferably in the range of 10 nm to 1 mm. The structure height is preferably in the range of 0.1 nm to 1 mm. Preferably, however, each embossed structure exhibits a microstructure and/or a nanostructure.

The size of a particular microscale or nanoscale surface element is, respectively, as the greatest extension in any direction parallel to the surface, i.e., the diameter of a cylindrical surface element or the diagonal of the base surface of a pyramidal surface element. is defined In the case of surface elements having macroscale extensions in one or more directions in (or parallel to) the surface and microscale or nanoscale extensions in one or more other directions within the surface, the term size of the surface element refers to the size of such surface. Refers to microscale and/or nanoscale extensions of an element. The length of a particular microscale or nanoscale surface element is defined as an extension in the longitudinal direction of the structured surface, respectively. Likewise, the width of a particular microscale or nanoscale surface element is defined as an extension in the width direction of the structured surface, respectively.

The height of the protruding (or raised) surface element is defined by a respective extension line measured from the adjacent floor surface on which the respective raised surface element is arranged, in a direction perpendicular to this floor surface. Likewise, the depth of the surface element extending downward from the exposed surface of the adjacent top is defined by the respective downward extension measured from the surface of the adjacent top from which the indentation extends in a direction perpendicular to the surface of this top.

The distance between two adjacent surface elements is defined as the distance between each two maxima or two relative maxima between these surface elements in a direction into the structured surface. A structured surface having a regular permutation of surface elements in one or more given directions parallel to the surface may be characterized by one or more pitch lengths in that direction. The term pitch length in a particular direction parallel to a surface denotes the distance between corresponding points of two adjacent, regularly repeating surface elements. wherein the surface elements both extend macroscale essentially parallel to one another in a first longitudinal direction and each have a microscale and optionally nanoscale cross-section in a direction normal to said longitudinal direction. may be illustrated for a structured surface comprising alternating permutations of rail-like surface elements. The pitch length of this structured surface in the direction normal to the longitudinal direction is the sum of the width of the channel-shaped surface element and the width of the rail-shaped surface element in this normal direction.

Preferably, each microstructured and/or nanostructured surface to be transferred by embossing advantageously ranges from 10 nm to 1000 μm, preferably from 10 nm to 500 μm, more preferably from 25 nm to a structure width in the range of 400 μm, very preferably in the range of 50 nm to 250 μm, more particularly in the range of 100 nm to 100 μm, and advantageously in the range of 10 nm to 1000 μm, preferably in the range of 10 nm to 500 Microscale and/or nanoscale with a structure height in the range of μm, more preferably in the range from 25 nm to 400 μm, very preferably in the range from 50 nm to 300 μm, more particularly in the range from 100 nm to 200 μm contains the surface elements of These dimensions apply to the embossing structure of both the composite (S1C1) and the composite (C2S2) and the coating (C2), as well as of course the embossing mold (e1) in the optional step (7).

The structure width and structure height of each surface comprising microstructured and/or nanostructured surface elements preferably produces a cross-section of the surface, and the structure height and structure width of said cross-section are subjected to optical and/or scanning electron microscopy. determined by deciding

The composite (S1C1) provided in step (1) of the method of the present invention can be prepared by various processes, for example, lithographic methods such as nanoimprint lithography, laser lithography and photolithography. It is preferred to prepare the complex (S1C1) by steps (6) to (9) as specified in more detail below.

Composite (S1C1), preferably used as embossing mold (e2) in steps (3-i) and (2-ii), consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1) ) is also referred to herein as "master substrate" or "master film". In case the substrate S1 is a film, the corresponding master film is referred to as "master foil". In case the substrate S1 is a web of foil, the corresponding master film is referred to as a "master foil web". In the following, the coating (C1) of the master film is also referred to as “at least partially cured master coating” or “master coating film”, and the coating composition (C1a) used to prepare the cured master coating is referred to as “master coating” " is referred to as Preferably there is no additional (coating) layer between (S1) and (C1) in the composite (S1C1). However, it is also possible for at least one adhesion promoter layer to be present between (S1) and (C1) of the composite (S1C1), in which case said layer is preferably transparent to UV radiation.

Steps (2-i) and (3-i)

After step (1), in a first alternative, the coating composition (C2a) is at least partially applied to the substrate (S2) to provide a composite (S2C2a), followed by using the composite (S1C1) to the coating composition of the composite (S2C2a) (C2a) is at least partially embossed to give the composite (S1C1C2S2). This first alternative to the process of the invention by steps (2-i) and (3-i) is described herein.

Step (2-i)

Step (2-i) of the method of the present invention provides for applying a radiation-curable coating composition (C2a) to at least a portion of the surface of the substrate (S2) to provide a composite (S2C2a).

Substrate (S2) represents the carrier material for the coating composition (C2a) or coating (C2) to be applied thereto. The substrate (S2) or, if a coated substrate is used, the layer located on the surface of the substrate (S2) and in contact with the coating composition (C2a) is preferably at least one thermoplastic polymer, more particularly polymethyl (meth) acrylates, polybutyl (meth)acrylates, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyvinylidene fluoride, polyvinyl chloride, polyesters such as polycarbonate and polyvinyl acetate; Preferably polyesters such as PBT and PET, polyamides, polyolefins such as polyethylene, polypropylene, polystyrene, and also polybutadiene, polyacrylonitrile, polyacetal, polyacrylonitrile-ethylene-propylene-diene-styrene copolymer (A-EPDM), polyimide (PI), polyetherimide (PEI), cellulose triacetate (TAC), phenolic resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyurethane, such as a thermoplastic polyurethane ( TPU), polyether ketones, polyphenylene sulfides, polyethers, polyvinyl alcohols, and mixtures thereof. Particularly preferred substrates or layers on their surfaces are polyolefins such as, for example, which may alternatively be isotactic, syndiotactic or atactic and may alternatively be unoriented or oriented via uniaxial or biaxial stretching, PP (polypropylene), SAN (styrene-acrylonitrile copolymer), PC (polycarbonate), PMMA (polymethyl methacrylate), PBT (poly (butylene terephthalate)), PA (polyamide) , ASA (acrylonitrile-styrene-acrylic acid ester copolymer) and ABS (acrylonitrile-butadiene-styrene copolymer), and also physical mixtures (blends) thereof. Particular preference is given to PP, SAN, ABS, ASA, and also blends of ABS or ASA with PA or PBT or PC. Particular preference is given to PET, PBT, PP, PE, and polymethyl methacrylate (PMMA) or impact-modified PMMA. Particular preference is given to polyester, most preferably PET, for use as material for the substrate S2. Alternatively, the substrate S2 itself can be made of various materials, such as glass, ceramic, metal, paper and/or textile, optionally even when a layer of at least one of the aforementioned polymers is applied to the substrate. have. In this case, the substrate S2 is preferably a plate and can be used, for example, in a roll-to-plate (R2P) embossing apparatus.

The coating composition (C2a) is advantageously irradiated through the substrate (S2) or the composite (S1C1), preferably through the substrate (S2). Accordingly, the transmittance of the substrate (S2) to radiation preferably corresponds to the maximum absorption or at least the absorption range of the at least one photoinitiator used in the coating composition (C2a). A further layer which is preferably transparent to UV radiation, for example an adhesion promoting layer, may be present in the composite (S2C2a) between (S2) and (C2a). However, it is advantageous if there is no additional layer between (S2) and (C2a) in the composite (S2C2a). Alternatively, if radiation is provided to the coating composition (C2a) through the composite (S1C1), the substrate (S2) may also be non-transmissive to the applied radiation, such as UV radiation. Additionally, the substrate (S2) may also be formed from (i) a single or double-sided adhesive tape optionally comprising a release liner or (ii) a polymeric substrate or self-adhesive polymeric substrate coated on one side with a self-adhesive layer. can be selected.

The thickness of the substrate S2 is preferably 2 μm to 5 mm. A layer thickness of 25 to 1000 μm, more particularly 50 to 300 μm, is particularly preferred.

The substrate S2 is preferably a film, more preferably a film web, very preferably a continuous film web. In this case, the substrate S2 can preferably be used in a roll-to-roll (R2R) embossing device or a plate-to-roll (P2R) embossing device.

In the context of the present invention, the term “continuous film” or “continuous film web” refers to a film having a length of preferably from 100 m to 10 km.

when step (2-i) is carried out (and preferably also when steps (3-i), (4) and (5-i) of the process are carried out, and also when step (2) of the process of the invention is carried out If -ii), (3-ii), (4) and (5-i) or (5-ii) are carried out), the substrate S2 is preferably in motion and thus is a moving substrate. During the execution of steps (2-i) and (3-ii), the substrate S2 is preferably moved by a conveying device such as a conveyor belt. Accordingly, the corresponding device used for carrying out step (2-i) and also step (3-ii) preferably comprises such a conveying device. The corresponding apparatus used to carry out step (2-i) further comprises means for applying the coating composition (C2a), preferably radiation-curable, to at least a part of the surface of the substrate (S2). A similar description applies to the corresponding apparatus used to carry out step (3-ii) and optional steps (6) to (9).

The coating composition (C2a) provided in steps (2-i) and (2-ii) of the method of the present invention may be any kind of coating composition as described below. Advantageously, the coating composition (C2a) applied in steps (2-i) and (2-ii) has a thickness of at least 0.5 μm, preferably at least 1 μm to 1,000 μm, more preferably at least 5 μm to 1,000 μm. The dry film thickness is applied.

Advantageously, the coating composition (C2a) applied in steps (2-i) and (2-ii) is at least 0.5 μm, preferably 5 to 1,000, determined according to procedure 12A of DIN EN ISO 2808:2007-05 a dry film thickness of μm, more preferably 6 to 900 μm, even more preferably 7 to 700 μm, in particular 8 to 500 μm, particularly preferably 9 to 400 μm, in particular 10 to 300 μm. In the sense of the present invention, the dry film thickness is preferably above the projections of the embossing structure, preferably comprising micro-scale and/or nano-scale surface elements of the surface of the coating (C2) or similarly of the coating (C1). The film thickness of the dry film is indicated.

Step (3-i)

Step (3-i) of the method of the present invention comprises at least partially embossing the coating composition (C2a) at least partially applied to the surface of the substrate (S2) by means of a composite (S1C1), as a product of at least partial embossing It is provided to provide a composite (S1C1C2aS2), wherein the composite (S1C1) is preferably used as an embossing mold (e2) of an embossing tool (E2), the composite (S1C1) being at least partially embossed with a substrate (S1) and at least partially of the cured coating (C1). The composite (S1C1) preferably used as the embossing mold (e2) can be pre-wetted with the coating composition (C2a) before the composite (S1C1) comes into contact with the coating composition (C2a) to be embossed.

At least partial embossing at least partially transfers the embossing structure to the surface of the coating composition (C2a) applied to the substrate (S2). The term "embossing" refers to a process in which, after steps (3-i) and (4), at least a part of the surface of the coating composition (C2a) as part of the composite (S2C2) exhibits an embossing structure. In this case, at least a predetermined area of the coating composition (C2a) of the composite (S2C2) is provided with an embossing structure. Preferably, the entire surface of the coating composition (C2a) of the composite (S2C2) is provided with an embossing structure. A similar description applies to the term “embossing” in relation to steps (2-ii) and (4) of the process of the invention and the optional steps (7) and (8) giving the complex (S1C1). The features or structures embossed with the coating composition (C2a) (or the coating composition (C1a) in the context of providing the composite (S1C1)) thereby are mirror images of the structured surface of the embossing mold. In the method of the invention, the embossed structure of the composite (S1C1) is transferred to the coating composition (C2a) or, after at least partial curing, to the coating (C2), wherein the composite (S1C1) is preferably an embossing tool (E2) used as an embossing mold (e2). Thus, the structure embossed with the coating composition (C2a) comprises the embossed structure of the substrate (S1) and at least one surface of the composite (S1C1) comprising the at least partially cured and at least partially embossed coating composition (C1). mirror image. Thus, the phase of the embossed surface of the at least partially embossed coating composition (C2a) and the at least partially cured and partially embossed coating composition (C2) may correspond to the phase of the embossing mold (e1), wherein An embossing mold (e1) was used for embossing the coating composition (C1a) of the composite (S1C1), as described below.

Step (3-i) preferably transfers the microstructures and/or nanostructures as embossed structures onto the coating composition (C2a).

A corresponding device preferably used for carrying out step (3-i) (and analogously steps (2-ii) and (3-ii) of the method) comprises a coating composition applied at least partially to the surface of the substrate (S2) ( means for at least partially embossing C2a) by means of at least one embossing tool (E2) comprising at least one embossing mold (e2). A device preferably used is, after application of the radiation-curable coating composition (C2a) to (S2), the embossing mold (e2) of the embossing tool (E2), ie the composite (S1C1), preferably in the form of a continuous film web. further comprising means for pressing onto the substrate (S2) used as is placed on

If necessary, step (3-i) may be performed at an elevated temperature, for example at 30°C to 100°C or 80°C. In this case, the composite (S2C2a) first moves through the heating roll mechanism before the actual embossing procedure, i.e. curing while in contact with the embossing tool (E1) is carried out, optionally by irradiation with infrared light. goes on After embossing and curing, the embossed composite (S2C2) optionally moves through a chill roll mechanism for cooling. Alternatively, curing can also be effected under cooling: in this case, the composite for embossing (S2C2a) first moves through a chill roll mechanism before the actual embossing procedure described above is carried out. Instead of using a separate heating or curing roll mechanism, it is also possible to heat or cool the embossing tool E2.

Accordingly, the corresponding apparatus preferably used for embossing the coating composition (C2a) applied to the substrate (S2) preferably comprises the following means:

(a) conveying means for conveying the substrate S2, preferably a conveyor belt;

(b) means for applying a coating composition (C2a), preferably radiation-curable, to at least a part of the surface of the moving substrate (S2);

(c) an embossing tool comprising at least one embossing mold (e2), preferably arranged downstream of the means for applying the radiation-curable coating composition (C2a), when viewed in the transport direction of the substrate (S2) ( E2), an embossing tool (E2) optionally comprising means for pressing the embossing mold (e2) of the embossing tool (E2) onto the substrate (S2);

(d) a heating roll mechanism optionally in combination with means for heating, preferably means for IR radiation,

(e) optionally means for cooling, preferably a cooling roll mechanism, and

(f) means for radiation, preferably UV radiation.

The embossing tool E2 may preferably be an embossing calender, which preferably comprises a grid application mechanism, more preferably a grid roll mechanism. Such calenders preferably have counter-rotating rolls arranged one above the other at certain intervals in the height direction, the rolls being fed with a composite (S2C2a) on which the embossing structure is to be provided, variably adjustable It is guided through a roll nip formed by the nip width. The grid roll mechanism here is preferably a first roll such as a metallic roll, for example a steel roll, a steel roll coated with a metal layer optionally containing a small amount of phosphorus such as a layer of copper or nickel, or optionally containing a small amount of phosphorus rolls coated with nickel sleeves, or else quartz-based rolls. Alternatively, however, a soft material such as for example rubber or polydimethylsiloxane (PDMS) may also be used as first roll or the roll may be coated with at least one soft material such as rubber or PDMS. Furthermore, rolls coated with at least one plastic may be used. Furthermore, the grid roll mechanism comprises a second roll, which is preferably a pressing roll made of steel, or a roll coated with at least one plastic or soft material such as rubber or PDMS. The second roll serves as a stamping or pressing roll. The composite to be embossed (S2C2a), for example in the form of a film web that is at least partially coated with the coating composition (C2a), is moved by means of a second roll or a pressing roll opposite to the first roll. At the point of the roll nip formed by counter-rotating rolls arranged at a certain distance from each other, the embossing according to step (3-i) is effected. Here, the first roll carrying the composite (S1C1) as the embossing mold (e2) serves to emboss the composite (S2C2a) guided by the second roll opposite to the embossing roll, wherein the second roll is The composite (S2C2a) to be provided with the embossing structure is pressed against the first embossing roll. By this step in step (3-i) or (2-ii) of the method, the mirror image of the embossed structure of the surface of the coating (C1) of the composite (S1C1) is on the surface of the coating composition (C2a) of the composite (S2C2a) are transcribed

During the execution of step (3-i), the embossing tool (E2) comprising the embossing mold (e2) is preferably at least partially pressed onto the applied coating composition (C2a).

The composite (S1C1) can be used as a reusable continuous embossing mold (e2) of the embossing tool (E2), preferably in the method of the present invention the method consists essentially of steps (5-i) or (5-ii) A very effective separation between the composite (S1C1) and the at least partially cured and at least partially embossed coating (C2), optionally applied to the substrate (S2), comprising a structured surface, when comprising is possible make it Step (3-i) preferably transfers the microstructures and/or nanostructures of the dimensions described above with respect to the complex (S1C1) provided in step (1).

The embossing mold (e2), ie advantageously composite (S1C1), preferably comprises a film web as substrate (S1), which comprises at least partially embossed and at least partially cured coating (C1). Particularly preferably the substrate (S1) is a continuous film web, which comprises at least partially embossed and at least partially cured coating (C1), thereby continuously embossing the composite (S1C1) used as embossing mold (e2) made into a mold, especially if the substrate S2 is also a continuous film web.

Steps (2-ii) and (3-ii)

After step (1), as an alternative to steps (2-i) and (3-i), the coating composition (C2a) is also first at least partially applied to the composite (S1C1), thereby at least partially embossed. Next, optionally the substrate (S2) is applied at least partially to the surface formed by the coating composition (C2a). This second alternative of the process of the invention by steps (2-ii) and (3-ii) compared to the first alternative of the process of the invention comprising steps (2-i) and (3-i) This is described here.

Step (2-ii)

Step (2-ii) of the method of the present invention comprises applying at least one coating composition (C2a) to at least a portion of the at least partially embossed and at least partially cured surface of the composite (S1C1), and applying the composite (S1C1) at least partially embossing the coating composition (C2a) using

The composite (S1C1) preferably used as the embossing mold (e2) of the embossing tool (E2) can optionally be pre-wetted prior to application of the coating composition (C2a).

The coating composition (C2a) provided in steps (2-i) and (2-ii) of the method of the present invention may be any kind of coating composition as described below, preferably a radiation-curable coating composition. Advantageously, the coating composition (C2a) applied in steps (2-i) and (2-ii) has a dry layer thickness of at least 0.5 μm, preferably at least 1 μm, more preferably at least 5 μm to 1,000 μm. is applied as

Substrate (S1) of the composite (S1C1) by applying, by step (2-ii), a coating composition (C2a), preferably radiation-curable, to at least a part of the at least partially embossed surface of the composite (S1C1) The desired phase (mirror image) of the at least partially embossed and at least partially cured coating (C1) of the phase is transferred from the composite (S1C1) to the coating composition (C2a) and after the execution of step (4) to the coating (C2) will be The composite (S1C1) thus functions not only as carrier material for (C2a) or (C2), but also as an embossing mold, preferably as an embossing mold (e2) of the embossing tool (E2).

The at least partial embossing in step (2-ii) is preferably effected by pressing the applied coating composition (C2a) onto the composite (S1C1) which is advantageously used as an embossing mold (e2) of an embossing tool (E2). The application of the pressure can be effected after application of the coating composition (C2a) by means such as, for example, a roll or grid roll mechanism comprising at least one roll. Typically the applied pressure ranges from 1 to 10 bar, preferably from 2 to 8 bar, more preferably from 3 to 7 bar. The grid roll mechanism here is preferably a metallic roll, for example a steel roll, a metal layer optionally containing a small amount of phosphorus, such as a copper layer, a steel roll coated with a nickel layer, or a nickel optionally containing a small amount of phosphorus. rolls coated with sleeves, or else quartz-based rolls, or rolls coated with at least one plastic, rubber or silicone, such as PDMS. Optionally, at least during the embossing and curing in steps (2-ii) to (4), as well as during step (5) advantageously to protect the coating composition (C2a) from oxygen and mechanical influences, The coating composition (C2a) can be temporarily lined with foil. The composite (S1C1C2) is advantageously provided after removal of the temporarily applied foil, having a thickness of 5 μm to 250 μm. Suitable materials for the temporarily applied foil are selected from the same materials which can also be used to prepare the substrate S2 as described above. Reference is hereby expressly made to the corresponding paragraph. Alternatively, the foil may be selected from cellulose triacetate (TAC) or a material typically found as a release liner. Advantageously, the temporarily applied foil consists of PET or TAC.

Step (3-ii)

Step (3-ii) of the method of the present invention provides for optionally applying a substrate (S2) to at least a portion of the surface formed by the coating composition (C2a) of the composite (S1C1C2a) to provide a composite (S1C1C2aS2) .

Preferably, the composite (S1C1) advantageously used as the embossing mold (e2) in step (2-ii) is obtained by applying the coating composition (C2a) to at least a part of its at least partially embossed surface to obtain the composite (S1C1C2a) ), being guided over the first roll as part of the embossing tool E2 during the execution of step (3-ii), the substrate S2 used in step (3-ii) facing the first roll and is guided through a second roll counter-rotating or co-rotating, preferably counter-rotating therewith.

The at least partial embossing according to step (3-ii) is preferably carried out at the level of the roll nip formed by two mutually opposed rolls rotating in the opposite or co-direction (in the same direction), wherein the composite The coating composition (C2a) of (S1C1C2a) faces the substrate (S2). In this case, the at least partial embossing is preferably achieved by pressing or pressing the substrate S2 onto the composite S1C1C2a, for example by means of a second roll or pressing roll.

Corresponding apparatus described above, preferably used for carrying out steps (2-i) and (3-i) of the method, likewise perform steps (2-ii) and (3-ii) of the method in a basically similar manner It can also be used for execution.

Step (4)

After steps (2-i) and (3-i) in the first alternative of the method of the invention, or after steps (2-ii) and (3-ii) in the second alternative of the method of the invention, Step (4) of the process of the invention comprises, at least partially, the at least partially embossed coating composition (C2a), optionally applied to the substrate (S2), obtained after step (3-i) or (3-ii) at least partially curing in contact with the composite (S1C1) preferably used as an embossing mold (e2) throughout the duration of the continuous curing to provide a composite (S1C1C2) or (S1C1C2S2).

In step (4), the applied coating composition (C2a) is at least partially cured to provide an at least partially embossed and partially cured coating material, which optionally comprises a substrate (S2). The term “at least partially cured” in relation to the coating composition (C2a) means that said coating composition (C2a) has been transformed into a film by at least a part of the coating composition, resulting in further processing or handling of the formed coating (C2), such as for example a post-exposure step to increase the double bond conversion ratio or transition to a state that enables the removal of the coating (C2) as part of the complex (S2C2) or as a self-supporting film (C2) .

Preferably throughout the duration of the at least partial curing in step (4), for pressing or for pressing the applied coating composition (C2a) onto the at least one composite (S1C1) which is advantageously used as an embossing mold (e2) (2-i) and (3-i) or the means used in steps (2-ii) and (3-ii) contact the coating composition (C2a) and/or the at least partially cured coating (C2) formed therefrom is doing

Step (3-i) or steps (2-ii) and (3-ii) and step (4) are preferably carried out simultaneously. In this case, the at least partial curing according to step (4) is preferably carried out in situ during the execution of step (3-i).

Accordingly, the corresponding apparatus preferably used for carrying out step (4) preferably comprises at least one radiation source for irradiating the coating composition (C2a) with curable radiation. Since the coating composition (C2a) is preferably a UV-curable coating composition, the curable radiation used is preferably UV radiation. If the coating composition (C2a) is not radiation-curable, it is preferably chemically curable. In this case, the curing in step (4) is effected thermally, for example using a suitable thermal radiation source. Of course, combined curing, ie thermal curing and curing with UV radiation, is also possible.

Examples of suitable radiation sources for radioactive curing are low, medium and high pressure mercury emitters and also fluorescent tubes, pulsed emitters, metal halide emitters (halogen lamps), lasers, LEDs and moreover electronic flash installations which enable radiative curing without photoinitiators or Includes an excimer emitter. Radiative curing is effected through exposure to high-energy radiation, ie UV radiation or sunlight, or by collision with high-energy electrons. A radiation dose that is typically sufficient for crosslinking in the case of UV curing is in the range of 80 to 3000 mJ/cm ² . It is of course also possible to use two or more - for example 2 to 4 radiation sources for curing. Each of these radiation sources may also radiate in a different wavelength range.

The at least partial curing in step (4) is advantageously effected by irradiation penetrating the substrate S2 and/or the composite S1C1. Preferably, irradiation is carried out through the composite (S1C1). If in step (3-ii) no substrate is present and the composite (S1C1) is advantageously used as at least one embossing mold (e2) of the embossing tool (E2), irradiation is preferably performed as a composite (S1C1) used as a substrate ) through the In both of these cases, (i) a single or double-sided adhesive tape optionally comprising a release liner or (ii) a substrate (S2) or a self-adhesive polymeric substrate optionally comprising a self-adhesive layer on one side , and/or a further layer between the substrate (S2) and the coating composition (C2a), or the transmittance of the substrate (S1) of the composite (S1C1), preferably at least one used in the coating composition (C2a) It is advantageous to correspond to the maximum absorption or at least the absorption range of the photoinitiator. Thus, for example, the material PET as substrate S2, ie, for example a PET film, is transparent to radiation with a wavelength of less than 400 nm. Photoinitiators that generate radicals under such radiation are, for example, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate and phenylbis( 2,4,6-trimethylbenzoyl)phosphine oxide. Thus, in this case, preferably at least one such photoinitiator is present in the coating composition (C2a).

optional step (5-i) or (5-ii)

After step (4), an optional step (5-i) or (5-ii) is performed depending on the presence of the substrate S2. In a first alternative to the method of the invention defined by steps (2-i) and (3-i), the substrate S2 therefrom is essentially present. Accordingly, only the optional step (5-i) may be applicable. In a second alternative of the method of the invention defined by steps (2-ii) and (3-ii), in step (3-ii) the optional substrate (S2) is applied to the surface formed by the coating composition (C2a). The optional step (5-i) may be applicable if it has been applied to at least a portion, but only the step (5-ii) may be applicable here if the optional substrate (S2) has not been applied in the step (3-ii).

Steps (5-i) and (5-ii) in the process of the invention are embossed coatings (C2) optionally applied to the substrate (S2), from the composite (S1C1) preferably used as the embossing mold (e2) is optionally removed to provide a composite (S2C2) consisting of a substrate (S2) and an at least partially embossed and at least partially cured coating (C2), or self-supporting if the optional substrate (S2) is not present providing a mold coating (C2), wherein the composite (S1C1) provided in step (1) of the method is restored. Preferably, step (5-i) or (5-ii) is carried out.

Said removal from the composite (S1C1) preferably used as an embossing mold (e2) results, for example, in the composite at least partially embossed and at least partially cured coating (C2), optionally applied to the substrate (S2). peeling from (S1C1) or vice versa. Peeling can be performed manually or using commonly known mechanical splitting means.

Alternatively, removal from the complex (S1C1) may comprise the following steps:

5-i-a) applying at least one adhesive layer (AL) on the surface of the substrate (S2) which is not in contact with the at least partially embossed coating (C2) to provide a composite (S1C1C2S2AL);

5-i-b) optionally, at least partially attaching the complex (S1C1C2S2AL) to the object (O1);

5-i-c) removing, preferably exfoliating, the complex (S1C1) from the complex (C2S2AL) optionally at least partially attached to the object (O1) or vice versa;

or

5-ii-a) applying at least one adhesive layer (AL) on at least a portion of the unstructured surface of the at least partially embossed coating (C2) to provide a composite (S1C1C2AL);

5-ii-b) optionally, at least partially attaching the complex (S1C1C2AL) to the object (O1);

5-ii-c) removing, preferably exfoliating, the complex (S1C1) from the complex (C2S2AL) optionally at least partially attached to the object (O1) or vice versa.

The adhesive layer (AL) can be, for example, a laminating adhesive, such as a polyacrylate or polyacrylate-based adhesive. However, the adhesive layer (AL) is preferably a self-adhesive layer or a multilayer construction. This self-adhesive layer can be applied by conventional methods such as laminating or spraying an adhesive. Said multilayer construction comprises, for example, an intermediate polymeric layer (PL), also called an inner-liner, which is coated on both surfaces with an adhesive (AH). Said adhesive (AH) may be a polyacrylate or polyacrylate-based adhesive, respectively. In principle, any type of polymer can be used to prepare the intermediate polymer layer (PL). Examples of such polymers are the polymers already described as substrate (S2). Explicitly refer to that paragraph. Preferred intermediate polymer layers (PL) are poly(meth)acrylates, polyesters such as PET and/or PBT, polyvinylidene fluoride, polyvinylchloride, polyamide and/or polyolefin. In particular, polyesters such as PET can be used. The layer thickness of the polymer layer (PL) may range from 5 to 55 μm, preferably from 6 to 50 μm, more preferably from 7 to 40 μm, in particular from 8 to 30 μm. Each adhesive (AH) may initially be covered with a release liner, such as silicone paper, for better handling. However, prior to use as the adhesive layer (AL) in step 5-i) or step (5-ii), one of the two release liners is removed. The other release liner is preferably removed in a subsequent step of the method of the invention, more preferably prior to at least partially attaching the composite (S1C1C2) or (S1C1C2S2) to the at least one object (O1). Therefore, before separating the composite (S1C1) from the coating (C2) or composite (C2S2) comprising the adhesive layer (AL), these composites are attached to the object (O1), and only after that the composite (S1C1) is attached to the object (O1) ) from the coating (C2) or composite (C2S2) at least partially attached via the adhesive layer (AL), preferably by peeling. Suitable objects (O1) can be made of a variety of materials including metals, plastics, reinforcements, glass, rubber, textiles, leather, paper, wood and mixtures thereof. Preferably, the at least one object O1 is a surface in contact with liquids and gases, such as aircraft, ships and automobiles, rotor blades, drilling platforms, pipelines, lighting systems, displays, photovoltaic modules, structural elements and decorations. selected from the group consisting of enemy elements.

Steps 5-i-a) and (5-i-b), or 5-ii-a) and 5-ii-b) are performed manually, or at least one conveying means for the adhesive layer (AL), at least partially embossed applying pressure to fix the adhesive layer (AL) on at least part of the unstructured surface of the coating (C2) or on the surface of the substrate (S2) that is at least partially in contact with the embossed coating (C2) at least one pressing means for, and preferably for removing the coating (C2) or the composite (S2C2) respectively from the composite (S1C1) which is advantageously used as an embossing mold (e2) of the embossing tool (E2) or vice versa may be performed by a machine comprising at least one dividing means for exfoliating.

Removal of the at least partially embossed and at least partially cured coating (C2) or composite (S2C2) respectively from the composite (S1C1) is preferably without destruction of the structured and embossed surface and the coating of the composite (S1C1) ( It is carried out easily without leaving significant residues on the surface of C1), preferably leaving no residues at all.

1 schematically shows a side view of an apparatus which can be used to carry out steps (1), (2-i) and (3-i) and also (4) and optionally (5-i) of the method of the present invention; and is used for exemplary description of the method of the present invention. This apparatus is also basically for carrying out steps (1), (2-ii) and (3-ii) and also (4) and optionally (5-i) or (5-ii) of the method of the present invention, can be used in a similar way, likewise. With this device it is possible to transfer structures such as preferably microstructures and/or nanostructures from the embossing molds (S1C1, e2) present as master films to the substrate (S2) coated with (C2a). Accordingly, this device is also generally referred to as a transfer device, and is given the reference numeral 10 in FIG. 1 .

The core of the transfer device 10 is an embossing area 1 in which a press roll 2 having a roll jacket made of fused silica is arranged. The press roll 2 is driven for rotation. A radiation source, which generates UV light, is arranged next to the press roll 2 , in particular in the form of an illumination unit 3 , which may comprise UV-LEDs arranged in a row in the longitudinal direction of the press roll 2 . As shown in FIG. 1 , the lighting unit 3 may also be arranged inside the press roll 2 . In the embossing area (1), a pressing roll (4) is arranged in such a way that it is pressed against a press roll (2). Two film web rollers 6 and 7 are arranged on the mold frame 5 of the transfer device 10, which can be motor-driven for rotation. Of course, the film web rollers 6 and 7 may also be mounted and arranged elsewhere other than the mold frame 5 , for example on a cabinet element or otherwise outside of the actual transfer device 10 . A master film web 8 , representing a continuous embossing mold, is rolled over film web rollers 6 and 7 , presented here as disposed on a mold frame. The master film web 8 is provided, as a surface asperity, on the transfer surface with a master coating layer (C1) featuring an inverted shape of microstructures and/or nanostructures to be transferred. Since the master coating layer (C1) is at least partially cured, the concave-convex structure in the layer is stable. The master film web 8 can be obtained by carrying out steps (6) to (9) of the method of the present invention, thereby constituting the composite (S1C1). The master film web 8 moves away from the first film web roller 6 and is fed to the embossing area 1 through a system of various deflection rollers and presses vertically from above, as shown in FIG . 1 . It moves to the area between the roll (2) and the pressing roll (4). In this region it is guided in taut contact over the peripheral section of the press roll 2 and then again exits the press roll 2 and once again through a deflection roller system accompanied by a web tensioner. 2 It is fed to the film web roller (7) and wound over it. A film web 9 forming a substrate S2, on which structures such as microstructures and/or nanostructures will be provided, starts from a film web roller 11, here again through various deflection roller systems accompanied by a web tightener. It is fed into the embossing area ( 1 ), where it moves taut over the peripheral section of the pressing roll ( 4 ), from here to the contact area of the pressing roll ( 4 ) and the press roll ( 2 ) or between these elements. into the formed roll nip area. 1 , the film web 9 exits vertically downward from this area and is led to the film web roller 12 - again through the deflection roller system and web tightener - over it as a fully processed product. winding up On its path to the roll nip between the embossing zone ( 1 ) or the press roll ( 2 ) and the pressing roll ( 4 ), the film web ( 9 ) has its surface facing the press roll ( 2 ) in the press zone ( 1 ). On top of this, a coating layer is provided in this case by means of a coating application unit 27 arranged outside of the press area 1 . Accordingly, the coating application unit 27 applies the coating composition (C2a) to the film web 9 used as (S2) according to step (2-i) of the method of the present invention. Then, in order to carry out step (3-i) of the method of the present invention, in the press area 1 , the film web 9 is provided with a coating layer in an uncured state by its surface, the master film web 8 ) of the master coating layer is merged with the provided surface. In this case, the film web 9 travels through the pressing roller 4 , and the master film web 8 travels through the press roll 2 . Both webs, ie film web 9 and master film web 8, have respective coating layers (in the case of master film web 8, an at least partially cured master coating layer corresponding to coating (C1); In the case of the film web 9, the surfaces provided with the uncured coating layer corresponding to the coating composition (C2a)) face each other. In the region where the pressing roll 4 presses against the press roll 2, the structure to be transferred formed on the master coating layer (C1), such as a microstructure and/or nanostructure inversion phase, a specific diameter corresponding to the coating composition (C2a) It is stamped with a layered coating, resulting in transfer of the structure. At the same time, the lighting unit 2 performs UV irradiation, and thus at least partial curing of the uncured coating layer corresponding to the coating composition (C2a) of the coating layer of the film web 9, the coating layer being the master It is carried out while still in contact with the coating layer (8). Accordingly, at least partial curing of the coating layer is carried out directly and in situ during the transfer of the structure. Irradiation of the film web 9 or of an uncured coating layer applied thereto is achieved here through the film material 9 in the case of irradiation from the outside into the press cylinder 2 . Alternatively, the irradiation is carried out through the fused silica material of the outer surface of the press cylinder 2 and also through the material of the master film web 8 and the master coating layer applied thereto. Accordingly, the master film web 8 and the master coating layer are designed to be transparent to the radiation used, in this case UV light. The outer surface of the press roll 2 is described herein as consisting of fused silica. However, any other material is also suitable here in principle as long as it is transparent to the curable radiation (which may be other than UV light) emitted from the inside of the press roll 2 . Alternatively, if the coating composition (C2a) is a non-radiation-curing coating composition, it is also possible to use, for example, a thermal emitter instead of the illumination unit 3 providing UV radiation. After at least partial curing by UV irradiation, there is the possibility of a post-exposure, for example with IR radiation. At the end of this curing operation, according to optional step (5-i) of the method of the present invention, the film web 9 and the master film web 8 are separated from each other, wherein the newly structured layer composite (S2C2) and the master The film S1C1 is separated. The coated film web 9 (ie, composite S2C2) thus provided with the desired structuring is fed as a finished product to a film web roller 12 and wound onto it. When irradiation is made from the outside to the press roll 2 by the lighting unit 3, the master film web 8 (ie, composite (S1C1)) and the film web 9 (ie, composite (S2C2)) are If an alternate arrangement is chosen, the coated film web 9 (ie, composite S2C2) provided with the desired structure may also be opaque. Then, the coating of the coating application unit 27 according to step (2-i) of the method of the present invention can be carried out without limitation of the operation on the master film web 8 .

Preparation of complex (S1C1):

The composite (S1C1) provided in step (1) of the method of the present invention can be prepared by various processes, for example, lithographic methods such as nanoimprint lithography, laser lithography and photolithography. It is preferred to prepare the complex (S1C1) by steps (6) to (9) as specified in more detail below. Accordingly, steps (6) to (9) of the method of the present invention are carried out to produce a composite (S1C1) which can be used as an embossing mold (e2) of the embossing tool (E2). Figure 2 provides an exemplary description of steps (6) to (9) of the process of the invention, which is also evident from the following description of this figure.

Optional steps (6) to (9) of the process of the present invention for preparing the complex (S1C1)

According to a preferred embodiment of the invention, the composite (S1C1) provided in step (1) of the method, consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1), comprises an embossing tool (E1) ) transferring the repeating and/or regularly arranged pattern of the embossing mold (e1) to the coating composition (C1a), at least partially curing the coating composition, and at least partially curing the structured and at least partially cured coating composition (i.e. The composite (S1C1)) is prepared by removing it from the embossing tool. Accordingly, the preferred complex (S1C1) provided in step (1) is obtained by the following steps:

(6) applying the radiation-curable coating composition (C1a) to at least a portion of the surface of the substrate (S1) to provide a composite (S1C1a);

(7) at least partially embossing the coating composition (C1a) at least partially applied to the surface of the substrate (S1) by means of at least one embossing tool (E1) comprising at least one embossing mold (e1);

(8) contacting the at least partially embossed coating composition (C1a), at least partially applied to the substrate (S1), with at least one embossing mold (e1) of the embossing tool (E1) throughout the duration of at least partial curing at least partially curing it in an intact state;

(9) removing the composite (S1C1) from the embossing mold (e1) of the embossing tool (E1) or vice versa to provide an at least partially embossed and at least partially cured composite (S1C1).

Step (6)

Step (6) of the method of the invention provides for applying the radiation-curable coating composition (C1a) to at least a part of the surface of the substrate (S1). The substrate (S1) constitutes the carrier material for the coating composition (C1a) or the coating (C1) respectively. Suitable materials for the substrate (S1) or its surface layer include the same materials, as described above, which can also be used to prepare the substrate (S2). Reference is hereby expressly made to the corresponding paragraph. A further layer, preferably transparent to UV radiation, for example an adhesion promoting layer, may be present in the composite (S1C1) between (S1) and (C1). However, it is advantageous if there is no additional layer between (S1) and (C1) in the composite (S1C1). The substrate S1 is advantageously a film web, preferably a moving film web or a continuous film web, more preferably a moving continuous film web. In this case, the substrate S1 can preferably be used in a roll-to-roll (R2R) embossing apparatus. A preferred material for the substrate (S1) is polyester, more particularly polyethylene terephthalate (PET). The thickness of the substrate S1 is preferably 2 μm to 5 mm. A layer thickness of 25 to 1000 μm, more particularly 50 to 300 μm, is particularly preferred.

The coating composition (C1a) provided in optional step (6) of the process of the invention is a radiation-curable coating composition as described in detail below. Advantageously, the coating composition (C1a) applied in step (6) is applied with a dry layer thickness of at least 0.5 μm, preferably at least 1 μm, more preferably at least 5 μm to 1,000 μm.

During the execution of step (6) (preferably also during the execution of steps (7), (8) and (9) of the method), the substrate S1 is preferably in motion and thus is a moving substrate. During the execution of step (6), the substrate S1 is preferably moved by means of conveying means such as a conveyor belt. Accordingly, the corresponding apparatus used to carry out step (6) preferably comprises conveying means of this kind. The corresponding apparatus used to carry out step (6) further comprises means for applying the coating composition (C1a), preferably radiation-curable, to at least a part of the surface of the substrate (S1).

Step (7)

Step (7) of the method of the invention comprises at least one embossing mold (e1), optionally pre-wetted with the coating composition (C1a), the coating composition (C1a) at least partially applied to the surface of the substrate (S1) embossing at least partially by means of at least one embossing tool (E1) having Said embossing mold (e1) may be a polymeric embossing mold (e1) or a metallic embossing mold (e1), preferably a metallic embossing mold (e1). Optionally, after the first composite (S1C1) is prepared, this first or preceding composite (S1C1) can be used as the embossing mold (e1). The at least partial embossing at least partially transfers the embossing structure to the surface of the coating composition (C1a) applied to the substrate (S1). The term "embossing" has been defined above, and reference is made explicitly to the corresponding paragraph.

Step (7) preferably transfers the microstructures and/or nanostructures of dimensions equal to the structure width and structure height as described above as embossed structures to the coating composition (C1a). Reference is made explicitly to the appropriate paragraph above.

Accordingly, the corresponding apparatus used to carry out step (7) is means for at least partially embossing by means of at least one embossing tool (E1) the coating composition (C1a) at least partially applied to the surface of the substrate (S1). includes A device preferably used is, after application of the radiation-curable coating composition (C1a) to (S1), an embossing mold (e1) as part of an embossing tool (E1), preferably a substrate used in the form of a continuous film web ( S1) further comprising means for pressing onto, said means being preferably arranged downstream of the means for applying the radiation-curable coating composition (C1a), viewed in the transport direction of the substrate (S1).

The at least partial embossing according to step (7) of the method of the invention is carried out by means of an embossing tool (E1). The embossing tool E1 may preferably be an embossing calender, which preferably comprises a grid application mechanism, more preferably a grid roll mechanism. Such calenders preferably have counter-rotating rolls arranged one above the other at specific intervals in the height direction, the rolls being fed with a composite (S1C1a) on which the embossing structure is to be provided, variably adjustable It is guided through a roll nip formed by the nip width. The grid roll mechanism here preferably comprises a first roll such as a metallic roll, for example a steel roll, a steel roll coated with a metal layer optionally containing a small amount of phosphorus such as a copper layer or a nickel layer, or optionally a small amount of phosphorus a roll coated with a nickel sleeve containing it, and a second roll. The first roll (embossing roll) as part of the embossing tool E1 contains an embossing mold e1 having a mirror image of the embossing structure to be embossed into the surface of the composite S1C1a. Thus, the phase of the structure of the embossing mold (e1) is the phase embossed into the coating composition (C2a) by means of the composite (S1C1) preferably used as the embossing mold (e2) in step (3-i) or (2-ii) corresponds to The second roll serves as a stamping or pressing roll. At the point of the roll nip formed by counter-rotating rolls placed at a certain distance from each other, embossing is effected. The embossing tool E1 used also has a mirror image of the embossing structure to be embossed into the surface of the composite S1C1a and is preferably a conventional press cylinder which can be pressed onto the composite S1C1a for at least partial embossing. It may be a metallic roll, for example a steel roll, made of a steel roll coated with a metal layer optionally containing a small amount of phosphorus such as a copper layer or a nickel layer. The mirror image consists of microstructured and/or nanostructured surfaces composed of microscale and/or nanoscale surface elements, as described above with respect to step (1). Reference is hereby expressly made to the corresponding paragraph. A mirror image of the structure to be embossed is produced on the embossing tool E1 according to a conventional method known to the person skilled in the art; Depending on the structure and material, certain methods may be particularly advantageous. The composite to be embossed (S1C1a), for example in the form of a film web at least partially coated with the coating composition (C1a), is moved by means of a second roll or a pressing roll counter-current to the first roll. At the point of the roll nip formed by counter-rotating rolls arranged at a certain distance from one another, the embossing according to step (7) is effected. Here, the first roll carrying the embossing mold e1 serves to emboss the composite S1C1a guided by the second roll opposite to the embossing roll, wherein the second roll is provided with an embossing structure The composite (S1C1a) is pressed against the first embossing roll. The embossing tool E1 is preferably a metallic embossing tool, more preferably made of steel, or a steel roll coated with a metal layer optionally containing a small amount of phosphorus, such as a copper layer or a nickel layer, or a small amount of phosphorus. A roll coated with an optionally containing nickel sleeve. Accordingly, the embossing mold (e1) is preferably metallic, more preferably made of steel, copper or nickel, and more particularly of nickel containing a small amount of phosphorus. However, alternatively, the embossing mold (e1) may be composed of a material such as silicone (i.e. polydimethylsiloxane (PDMS)), or a previously prepared composite (S1C1) is used as the embossing mold (e1) It is possible to augment the pattern originally made in the first embossing into the first composite (S1C1). Furthermore, rolls coated with at least one plastic may also be used. Furthermore, the embossing tool E1 can have a structured coating such as a UV coating as the embossing mold e1 .

If necessary, step (7) may be carried out at an elevated temperature, for example at 30°C to 100°C or 80°C. In this case, the composite (S1C1a) first moves through the heating roll mechanism before the actual embossing procedure, i.e. curing while in contact with the embossing tool (E1) takes place, and optionally irradiation with infrared light goes on After embossing and curing, the embossed composite (S1C1) optionally moves through a chill roll mechanism for cooling. Alternatively, curing can also be effected under cooling: in this case, the composite for embossing (S1C1a) first moves through a chill roll mechanism before the actual embossing procedure described above is carried out. Instead of using a separate heating or curing roll mechanism, it is also possible to heat or cool the embossing tool E1 .

Step 8

Step (8) of the method of the invention comprises at least partially embossed coating composition (C1a), applied at least partially to the substrate (S1), over the duration of at least partial curing of at least one of the embossing tools (E1) At least partially curing in contact with the embossing mold (e1) is provided.

Steps (7) and (8) are preferably performed simultaneously. In this case, curing according to step (8) is preferably carried out in situ during the execution of step (7).

Accordingly, the corresponding device used to carry out step (8) preferably comprises at least one radiation source for irradiating the radiation-curable coating composition (C1a) with curable radiation, preferably UV radiation.

Examples of suitable radiation sources for radiation curing have been described above in connection with the curing of the coating composition (C2a). Reference is hereby expressly made to the corresponding paragraph.

The curing in step (8) is preferably effected by irradiation penetrating the substrate (S1). In this case, it is advantageous if the transmittance of the substrate (S1) to the radiation used corresponds to that of the at least one photoinitiator contained in the coating composition (C1a). Thus, for example, the material PET as substrate S1, ie, for example a PET film, is transparent to radiation with a wavelength of less than 400 nm. Photoinitiators that generate radicals under such radiation are, for example, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate and phenylbis( 2,4,6-trimethylbenzoyl)phosphine oxide.

Step (9)

Step (9) of the method of the present invention removes the composite (S1C1) from the embossing tool (E1), thereby making it usable as the desired product, ie an embossing mold (e2), the substrate (S1) and at least partially embossing It provides for preparing a composite (S1C1) consisting of a processed and at least partially cured coating (C1).

Optionally, the composite (S1C1) or master film increases or maximizes the double bond conversion at the surface of the coating (C1) of the composite (S1C1), in particular after separation from the embossing mold (e1), so that the coating composition (C2a) ) with a suitable radiation source, such as a UVA lamp, to reduce or minimize covalent crosslinking. Any radiation source described above is suitable, reference is made explicitly to these preceding paragraphs.

Preferably, the surface of the at least partially cured and at least partially embossed coating (C1) of the composite (S1C1) is a microstructured and/or nanostructured surface.

2 shows an apparatus which can be used to carry out steps (6) to (9) of the method of the invention for producing a composite (S1C1) advantageously used as an embossing mold (e2), ie for producing a master film; schematically presents a side view, which is used for illustrative description of steps (6) to (9) of the method of the present invention. With this device, structures such as microstructures and/or nanostructures are transferred by means of an embossing tool (E1) to a substrate (S1) coated with (C1a) and, after at least partial curing, a composite ( It is possible to produce S1C1) - referred to in FIG. 2 as the master film web 8 , which composite can be used as an embossing mold e2 as described above in the method described in connection with FIG. 1 .

The master transfer device 30 shown in FIG. 2 operates according to the transfer principle, wherein the desired inversion structure is a master corresponding to the composite S1C1a from a structured press cylinder or press roll (here the master press cylinder 17 ). directly embossed with a coating layer in an as yet uncured state applied to the film web 8b, said coating layer being then at least partially cured together with the structure applied thereto to correspond to the composite S1C1 - a master film web 8 ), wherein the curing is carried out in situ by the lighting unit 3 . In this method, a film web 8a serving as substrate S1, containing only a carrier material, ie containing a pure film to which no master coating C1a has been applied, is drawn from a film web roller 18, It is guided through various deflection roller systems and web tensioning systems and introduced into the embossing area ( 1 ) of the machine. Here, the film web 8a is transferred from a coating application means 27 provided with a master coating layer (corresponding to the coating composition C1a), still in uncured state, to a pressing roll 4 and a master press cylinder 17 . Move to the press area in between. This coating application corresponds to step (6) of the process of the invention. In the embossing area (1), the master film web (8b) having the master coating layer (C1a) still in uncured state moves along a section of the outer surface of the master press cylinder (17), the master press cylinder (17) Microscale and/or nanoscale surface elements of the microstructured and/or nanostructured surface embossed into the outer surface of the master film web 8b are introduced and transferred as an inversion phase into the master coating layer of the web 8b. This corresponds to step (7) of the process of the invention. The master film web 8b comprising the uncured coating composition (C1a) is then at least partially cured according to step (8) of the process of the invention. The curing here is effected in situ by means of UV radiation via irradiation with the illumination unit 3 , for example by means of a UV-LED unit. The resulting master film (8), ie the composite (S1C1), is subsequently removed from the outer surface of the master press cylinder (17) according to step (9) of the method of the present invention, and thus the finished master film web ( 8) is wound over the film web roller (19). The film web roller 19 then contains a finished master film web 8 to which a master coating layer has been applied and embossed with a reversed phase of microstructure and/or nanostructure. This film web roller 19 can be removed and then used as the first film web roller 6 in the transfer apparatus 10 according to FIG. 1 or in another transfer apparatus operating on the same principle.

Coating compositions (C1a) and (C2a) used according to the invention

Coating composition (C1a)

The coating composition (C1a) is a radiation-curable coating composition. The terms “radiation-curable” and “radiation-curing” are interchangeable herein. The term “radiation-curing” preferably refers to electromagnetic and/or particulate radiation, for example visible to (N)IR light in the wavelength range of λ=400-1200 nm, preferably 700-900 nm, and/or by UV light in the wavelength range of λ=100-400 nm, preferably λ=200-400 nm, more preferably λ=250-400 nm, and/or electron radiation in the range of 150 to 300 keV, more preferably at least 80 mJ/cm ² , preferably with a radiation dose of 80 to 3000 mJ/cm ² radical polymerization of polymerizable compounds. Radiation curing is particularly preferably carried out using UV radiation. The coating composition (C1a) can be cured using a suitable radiation source. Accordingly, (C1a) is preferably a UV radiation-curing coating composition.

The coating composition (C1a) preferably comprises:

(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight and very preferably 100% by weight.

The coating composition (C1a) is present in a total amount of 5 to 45% by weight, preferably 8 to 40% by weight, more preferably 9 to 35% by weight, based on the total weight of the coating composition (C1a), of at least one at least 25 weights of at least one crosslinkable polymer and/or oligomer, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a); %, preferably at least 50% by weight, more preferably at least 90% by weight, very preferably 100% by weight is at least one silicone (meth)acrylate oligomer.

The term “oligomer” refers to a compound of relatively low molecular weight consisting of a small number, typically from 2 to less than 10, monomer units. The monomer units may be structurally identical, or they may be similar, or they may be different from each other. The oligomeric compound is typically a liquid at room temperature and ambient pressure of 23° C., wherein the kinematic viscosity at 23° C. measured according to DIN EN ISO 2555 (Brookfield method) is preferably less than 500 Pa*s; More preferably, it is less than 200 Pa*s. The term “crosslinkable” refers to a polymer or oligomer having, on average, at least one, preferably at least two, pendant unsaturated groups capable of forming free radicals for crosslinking reactions. The crosslinkable oligomeric and/or polymeric compound is preferably soluble in one or more reactive diluents.

The silicone (meth)acrylate oligomers or polymers useful in the present invention can typically be prepared by a condensation reaction between (meth)acrylic acid and a hydroxyfunctional silicone (eg α,ω-polydimethylsilicone diol). Silicone acrylates, due to their silicone backbone, improve the elasticity and elongation of structured surfaces, but tend to compromise their tensile strength and robustness. The more functional silicone (meth)acrylates are often used because of their low surface energy properties. Examples of useful silicone (meth)acrylates are evercryl from UCB Radcure Inc. under the trade name Sartomer (eg Sartomer CN 9800) from Sartomer Co. (EBECRYL) (eg Evercryl 350, Evercryl 1360) and as methacrylate X-22 (eg X-22 from Shin-Etsu Silicones Europe B.V.) -22-164, X-22-164A).

With particular preference the coating composition (C1a), based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a), is at least 25% by weight, preferably at least 50% by weight, more preferably preferably at least one silicone (meth)acrylate oligomer, preferably exactly one silicone (meth)acrylate oligomer in a total amount of at least 90% by weight, very preferably 100% by weight, more preferably from 2 to exactly one silicone (meth)acrylate oligomer comprising three unsaturated groups.

Besides silicone (meth)acrylates, other crosslinkable polymers and/or oligomers optionally present in the coating composition (C1a) are preferably (meth)acrylated oligomers or polymeric compounds, urethane (meth)acrylates, vinyl (meth)acrylates ) acrylates, epoxy (meth) acrylates, polyester (meth) acrylates, poly (meth) acrylates, polyether (meth) acrylates, olefin (meth) acrylates, (meth) acrylated oils, and their mixtures, preferably urethane (meth)acrylate oligomers. The coating composition (C1a) comprises from 0 to 75% by weight, preferably from 0 to 50% by weight, more preferably from 0 to 75% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a). said other crosslinkable polymers and/or oligomers in a total amount of 0 to 10% by weight, very preferably 0% by weight. In other words, the coating composition (C1a) very preferably comprises no other crosslinkable polymers and/or oligomers other than at least one silicone (meth)acrylate.

Urethane (meth)acrylates are obtainable, for example, by reaction of polyisocyanates with hydroxyalkyl (meth)acrylates and optionally chain extenders such as diols, polyols, diamines, polyamines or dithiols or polythiols . Urethane (meth)acrylates dispersible in water without the addition of emulsifiers additionally contain ionic and/or nonionic hydrophilic groups which are introduced into the urethane via synthetic components such as, for example, hydroxycarboxylic acids. These urethane (meth)acrylates contain essentially as synthetic components:

(a) at least one organic aliphatic, aromatic or cycloaliphatic di- or polyisocyanate;

(b) at least one compound having at least one isocyanate-reactive group, preferably a hydroxyl-bearing monomer, and at least one radically polymerizable unsaturated group, and

(c) optionally at least one compound having at least two isocyanate-reactive groups, for example polyhydric alcohols.

The urethane (meth)acrylates preferably have a number-average molar weight M _n of 200 to 20000, more particularly 500 to 10000, very preferably 600 to 3000 g/mol (using tetrahydrofuran as eluent and standard determined by gel permeation chromatography using polystyrene as water). The urethane (meth)acrylate contains preferably 1 to 5, more preferably 2 to 4 mol of (meth)acrylic groups per 1000 g of urethane (meth)acrylate.

Epoxide (meth)acrylates are obtainable by reaction of an epoxide with (meth)acrylic acid. Examples of contemplated epoxides include those of epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably aromatic or aliphatic glycidyl ethers. Examples of possible epoxidized olefins include ethylene oxide, propylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, vinyloxirane, styrene oxide or epichlorohydrin; Preference is given to ethylene oxide, propylene oxide, isobutylene oxide, vinyloxirane, styrene oxide or epichlorohydrin, particular preference to ethylene oxide, propylene oxide or epichlorohydrin, ethylene oxide and epichlorohydrin are particularly preferred. Aromatic glycidyl ethers include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol/dicyclopentadiene such as 2,5-bis[(2,3-epoxypropoxy)phenyl]octahydro-4,7-methano-5H-indene, tris[4-( 2,3-epoxypropoxy)phenyl]methane isomers, phenol-based epoxy novolacs and cresol-based epoxy novolacs. Aliphatic glycidyl ethers are, for example, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether , 1,1,2,2-tetrakis[4-(2,3-epoxypropoxy)phenyl]ethane, diglycidyl ether of polypropylene glycol (α,ω-bis(2,3-epoxypropoxy) ) poly(oxypropylene) (and diglycidyl ether of A of hydrogenated bisphenol (2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane)) Epoxide (meth) The acrylate preferably has a number-average molar weight M _n of from 200 to 20000, more preferably from 200 to 10000 g/mol, very preferably from 250 to 3000 g/mol; epoxide (meth)acrylate 1000 The amount of (meth)acrylic groups per gram is preferably 1 to 5, more preferably 2 to 4 (determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).

The (meth)acrylated poly(meth)acrylate is an α,β-ethylenically unsaturated carboxylic acid, preferably (meth)acrylic acid, obtainable by esterifying a poly(meth)acrylate polyol with (meth)acrylic acid; more preferably the corresponding esters of acrylic acid with polyacrylate polyols.

Carbonate (meth)acrylates with various functionalities are available. The number-average molecular weight M _n of the carbonate (meth)acrylate is preferably less than 3000 g/mol, more preferably less than 1500 g/mol, very preferably less than 800 g/mol (polystyrene as standard was determined by gel permeation chromatography using tetrahydrofuran as eluent). Carbonate (meth)acrylates are prepared by transesterification of a carbonic acid ester with a polyhydric, preferably dihydric alcohol (diol, for example hexanediol), as described for example in EP 0 092 269 A1, It is obtainable in a simple manner by subsequent esterification of the free OH groups with (meth)acrylic acid, or alternatively by transesterification with (meth)acrylic acid esters. They are also obtainable by reaction of phosgene, urea derivatives with polyhydric alcohols, for example dihydric alcohols. Also conceivable are reaction products of meth(acrylates) of polycarbonate polyols, such as one of the specified diols or polyols and carbonic esters and also hydroxyl-containing (meth)acrylates. Examples of suitable carbonic acid esters are ethylene, 1,2- or 1,3-propylene carbonate, dimethyl, diethyl or dibutyl carbonate. Examples of suitable hydroxyl-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylate, Neopentyl glycol mono(meth)acrylate, glyceryl mono- and di(meth)acrylate, trimethylolpropane mono- and di(meth)acrylate and also pentaerythritol mono-, di- and tri(meth)acrylic it is rate Preferably the carbonate (meth)acrylate is an aliphatic carbonate (meth)acrylate.

Particularly preferably the coating composition (C1a) is present in a total amount of from 5 to 45% by weight, preferably from 8 to 40% by weight, more preferably from 9 to 35% by weight, based on the total weight of the coating composition (C1a). at least one crosslinkable polymer and/or oligomer selected from the group consisting of: i) at least one silicone (meth)acrylate oligomer, preferably exactly one silicone (meth)acrylate oligomer, very preferably exactly one silicone (meth)acrylate oligomer comprising on average two to three unsaturated groups, and ii) a (meth)acrylated oligomer or polymer compound, urethane (meth)acrylate, vinyl (meth)acrylate, Epoxy (meth)acrylates, polyester (meth)acrylates, poly(meth)acrylates, polyether (meth)acrylates, olefin (meth)acrylates, (meth)acrylated oils, and mixtures thereof, preferably is another crosslinkable polymer and/or oligomer selected from urethane (meth)acrylate oligomers.

Therefore, particularly preferably, the coating composition (C1a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a), more preferably at least 90% by weight of at least one silicone (meth)acrylate oligomer in total, in particular exactly one silicone (meth)acrylate oligomer comprising on average 2 to 3 unsaturated groups, and the coating composition (C1a) Less than 75% by weight, preferably less than 50% by weight, more preferably less than 10% by weight of (meth)acrylated oligomers or polymer compounds, based on the total weight of all crosslinkable polymers and/or oligomers comprised in , urethane (meth) acrylate, vinyl (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, poly (meth) acrylate, polyether (meth) acrylate, olefin (meth) acrylic other crosslinkable polymers and/or oligomers selected from esters, (meth)acrylated oils, and mixtures thereof, preferably urethane (meth)acrylate oligomers.

The coating composition (C1a) comprises, based on the total weight of the coating composition (C1a), 40 to 85% by weight or 95% by weight, preferably 50 to 95% by weight or 85% by weight or 83% by weight, more preferably comprises at least one reactive diluent in a total amount of 55 to 83% by weight. Suitable reactive diluents are polymerizable with the polymer and/or oligomeric compound to form a master substrate comprising a copolymerized elastomeric network of cured master coating (C1). The term “reactive diluent” refers to a low molecular weight monomer capable of participating in a polymerization reaction to form a polymeric material. The weight average molecular weight M _w of this monomeric compound as determined by GPC is preferably less than 1000 g/mol, more preferably less than 750 g/mol.

Preferably, the reactive diluent is a free-radically polymerizable monomer and includes, for example, ethylenically-unsaturated monomers such as (meth)acrylate, styrene, vinyl acetate and mixtures thereof. Preferred monomers are (meth)acryloyl-functional monomers such as, for example, alkyl (meth)acrylates, aryloxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, N-vinyl compounds and their include combinations. Suitable monomers are known to the person skilled in the art and are listed, for example, in WO 2012/006207 A1.

A particularly preferred coating composition (C1a) comprises at least one polyfunctional ethylenically unsaturated monomer , ie a compound having at least two polymerizable double bonds in one molecule, as reactive diluent for increasing the crosslinking density. Representative examples of such polyfunctional monomers are listed, for example, in WO 2012/006207 A1. Particularly preferred reactive diluents are hexane diol diacrylate and/or at least two, preferably at least three, more particularly precisely, structural units of formula (I) which may be different from one another or may be at least partially identical to each other. are selected from compounds comprising:

here

The radicals R ¹ are, independently of one another, a C ₂ -C ₈ alkylene group, very preferably a C ₂ alkylene group,

The radicals R ² are, independently of one another, H or methyl,

parameter m independently of one another is an integer in the range from 1 to 15, very preferably from 1 to 4 or from 2 to 4, provided that in at least one of the structural units of formula (I) the parameter m is at least 2, preferably exactly 2 is With particular preference, the compound comprises three identical structural units of formula (I), wherein the parameter m is 2.

를 통해 부착된다. 이러한 결합은 바람직하게는 성분의 백본의 탄소 원자에 대한 라디칼 -[O-R¹]_m-의 산소 원자의 연결을 통해 이루어진다. 이로써, 화학식 (I)의 적어도 2개의 구조 단위가 단일 성분, 즉, 반응성 희석제 b) 내에 존재한다. 적합한 백본은, 예를 들어, 네오펜틸 글리콜, 글리세린, 트리메틸올프로판, 트리메틸올에탄 또는 펜타에리트리톨로부터 선택된다.All structural units of formula (I) have a symbol in the backbone of said reactive diluent.

is attached through This bonding is preferably effected via the connection of the oxygen atom of the radical -[OR ¹ ] _m - to the carbon atom of the backbone of the component. Thereby, at least two structural units of formula (I) are present in a single component, ie reactive diluent b). Suitable backbones are, for example, selected from neopentyl glycol, glycerin, trimethylolpropane, trimethylolethane or pentaerythritol.

The compound preferably comprises ether groups of the formula "-OR ¹ -" in a total number in the range of 4 to 18, more preferably in the range of 5 to 15, very preferably in the range of 6 to 12. The compound preferably has a number average molecular weight (M _n ) in the range from 300 to 2000 g/mol, more preferably from 400 to 1000 g/mol.

The compound preferably has exactly three structural units of the formula (I). In this case, the compound has exactly three functional (meth)acrylic groups. Alternatively, each structural unit of formula (I) may be present more than three times as part of said compound. In this case, for example, the compound may have more than 3 functional (meth)acryl groups, for example 4, 5 or 6 (meth)acryl groups.

The aforementioned radicals R ¹ are each independently of one another a C ₂ -C ₈ alkylene group, preferably a C ₂ -C ₆ alkylene group, more preferably a C ₂ -C ₄ alkylene group, very preferably each independently of one another an ethylene group and/or a propylene group, particularly preferably ethylene. In particular, all radicals R ¹ are ethylene. The radicals R ¹ having the structure -CH ₂ -CH ₂ -CH ₂ - or the structure -CH(CH ₃ )-CH ₂ - or the structure -CH ₂ -CH(CH ₃ )- are suitable in each case as propylene group . However, particular preference is given in each case to the propylene structure —CH ₂ —CH ₂ —CH ₂ —.

The parameter m is at each occurrence, independently of one another, an integer in the range from 1 to 15. Since the compound has at least 2, preferably at least 3 structural units of formula (I) and the parameter m is at least 2 in at least one of the structural units of formula (I), the compound has the formula "-OR ¹ -" comprises a total of at least 3, preferably at least 4 ether groups.

Preferably, the compound has a total of at least 5, more preferably at least 6 ether groups of the formula "-OR ¹ -". The number of ether groups of the formula "-OR ¹ -" in the compound is preferably in the range from 4 to 18, more preferably in the range from 5 to 15 and very preferably in the range from 6 to 12.

The total fraction of ether segments -[OR ¹ ] _m present in the structural units of the formula (I) of said compound is in each case at least 35% by weight, more preferably at least at least, based on the total weight of said compound 38% by weight, very preferably at least 40% by weight, even more preferably at least 42% by weight, even more particularly at least 45% by weight.

The compound has a number-average molecular weight (M _n ) determined by GPC, preferably in the range from 300 to 2000 g/mol, more preferably from 350 to 1500 g/mol, more particularly from 400 to 1000 g/mol .

Particularly preferred polyfunctional ethylenically unsaturated monomers are at least one compound of formula (IIa) and/or (IIb):

where, independently of each other in each case,

R ¹ and R ² and also m have the definitions given above with respect to structural unit (I), including the preferred embodiments specified above,

R ³ is H, C ₁ -C ₈ alkyl, OH or OC _1-8 alkyl, more preferably C ₁ -C ₄ alkyl, OH or OC _1-4 alkyl, very preferably C ₁ -C ₄ is alkyl or OH, or

R ³ is a radical -[OR ¹ ] _m -OC(=O)-C(R ² )=CH ₂ , wherein R ¹ , R ² and m are structural units, including the preferred embodiments thereof specified above, ( It has the definitions specified above in relation to I).

As a polyfunctional ethylenically unsaturated monomer as a reactive diluent,

the radicals R ¹ are each independently of the other a C ₂ -C ₈ alkylene group,

the radicals R ² are each independently of one another H or methyl,

The parameter m is in each case independently of one another in the range 1 to 15, preferably in the range 1 to 10, more preferably in the range 1 to 8 or 2 to 8, very preferably in the range 1 to 6 or 2 to 6 is an integer parameter in the range, more particularly in the range from 1 to 4 or 2 to 4, provided that in at least one, preferably in all of the structural units of formula (I), the parameter m is at least 2,

R ³ is C ₁ -C ₈ alkyl, OH or OC _1-8 alkyl, more preferably C ₁ -C ₄ alkyl, OH or OC _1-4 alkyl, very preferably C ₁ -C ₄ alkyl or OH

Particular preference is given to using at least one compound of formula (IIa).

Particularly preferred compounds comprising at least two structural units of formula (I) are neopentyl glycol, trimethylolpropane, trimethylolethane or a total of 4-fold to 20-fold or 4-fold to 12-fold alkoxylation. (meth)acrylates of pentaerythritol, such as ethoxylated, propoxylated or ethoxylated and propoxylated, more particularly exclusively ethoxylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol to be. Most preferred are the corresponding (meth)acrylates derived from alkoxylated trimethylolpropane. Products of this kind are commercially available, for example Sartomer® SR 499 and Sartomer® SR 502 and also Sartomer® SR 415 and Sartomer® SR 9035 and also Sartomer® SR 501 sold under the names have.

The coating composition (C1a) comprises at least one in a total amount of 40 to 95% by weight, preferably 50 to 85% by weight, more preferably 55 to 83% by weight, based on the total weight of the coating composition (C1a). reactive diluents, preferably hexane diol diacrylate and/or (meth)acrylate derived from 6-fold ethoxylated trimethylolpropane.

The coating composition (C1a) is, for curing by visible light to (N)IR light and/or UV light, from 0.01 to 15% by weight, preferably from 0.5 to 10% by weight, based on the total weight of the coating composition (C1a). at least one photoinitiator in a total amount of % by weight, more preferably 1 to 8% by weight. These photoinitiators can be decomposed into radicals that can ultimately initiate radical polymerization by the light of the irradiated wavelength. In contrast, in the case of curing by means of electron radiation, the presence of such a photoinitiator is not required. Preferably the coating composition (C1a) comprises at least one photoinitiator which can be decomposed by light of the irradiated wavelength into radicals which can ultimately initiate radical polymerization.

Photoinitiators such as UV photoinitiators are known to the person skilled in the art. Examples of those contemplated are phosphine oxides such as (alkyl)-benzoylphenylphosphine oxides, benzophenones, α-hydroxyalkyl aryl ketones, thioxanthones, anthraquinones, acetophenones, benzoins and benzoin ethers, ketals, imidazoles or phenylglyoxylic acids, and mixtures thereof.

Phosphine oxides are, for example, monoacyl- or bisacylphosphine oxides, for example diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl (2,4,6-trimethyl benzoyl)phenylphosphinate, phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide or bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide . Benzophenones are, for example, benzophenone, 4-aminobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, Michler's ketone. , o-Methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2,4-dimethylbenzophenone, 4-isopropylbenzophenone, 2-chlorobenzophenone, 2,2'- dichlorobenzophenone, 4-methoxybenzophenone, 4-propoxybenzophenone or 4-butoxybenzophenone; α-hydroxyalkyl aryl ketones include, for example, 1-benzoylcyclohexan-1-ol (1-hydroxycyclohexyl phenyl ketone), 2-hydroxy-2,2-dimethylacetophenone (2-hydroxy -2-methyl-1-phenylpropan-1-one), 1-hydroxyacetophenone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane A polymer containing -1-one or 2-hydroxy-2-methyl-1-(4-isopropen-2-ylphenyl)propan-1-one in copolymerized form. Xanthone and thioxanthone are, for example, 10-thioxanthenone, thioxanthen-9-one, xanthene-9-one, 2,4-dimethylthioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone or chloroxanthenone; Anthraquinones include, for example, β-methylanthraquinone, tert-butylanthraquinone, anthraquinonecarboxylic acid ester, benz[de]anthracen-7-one, benz[a]anthracene-7,12-dione, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone or 2-amylanthraquinone. Acetophenones are, for example, acetophenone, acetonaphthoquinone, valerophenone, hexanophenone, α-phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morphol Nobenzophenone, p-diacetylbenzene, 4'-methoxyacetophenone, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 3-acetylphenanthrene, 3-acetylindole, 9-fluoro Lenone, 1-indanone, 1,3,4-triacetylbenzene, 1-acetonaphthone, 2-acetonaphthone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino Propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-2-one or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one to be. Benzoins and benzoin ethers are, for example, 4-morpholinodeoxybenzoin, benzoin, benzoin isobutyl ether, benzoin tetrahydropyranyl ether, benzoin methyl ether, benzoin ethyl ether, benzoin phosphorus butyl ether, benzoin isopropyl ether or 7H-benzoin methyl ether. Ketals are, for example, acetophenone dimethyl ketal, 2,2-diethoxyacetophenone or benzyl ketals such as benzyl dimethyl ketal. Typical mixtures are, for example, 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexyl phenyl ketone, bis(2,6-dimethoxybenzoyl)(2,4, 4-trimethylpentyl)phosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone and 1-hydroxycyclohexylphenyl ketone, bis(2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl)phosphine oxide and 1-hydroxycyclohexyl phenyl ketone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4,6-trimethylbenzophenone and 4-methylbenzophenone and diphenyl (2,4,6- trimethylbenzoyl)phosphine oxide.

Particularly preferred photoinitiators are diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, phenylbis(2,4,6-trimethylbenzoyl)phosphine Pin oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 1-benzoylcyclohexan-1-ol , 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof. Commercially available photoinitiators are, for example, Irgacure® 184, Irgacure® 500, Irgacure® TPO, Irgacure from IGM Resins B.V. ® TPO-L and Lucirin® TPO and also Darocure® 1173.

The coating composition (C1a) may optionally further comprise at least one additive . The concept of additives is known to the person skilled in the art, for example, from Roempp Lexikon "Lacke und Druckfarben", Thieme Verlag, 1998, page 13. A preferred additive used is at least one rheological additive. The term is also known to the person skilled in the art, for example, from Roempp Lexikon "Lacke und Druckfarben", Thieme Verlag, 1998, page 497. The terms “rheological additive”, “rheological additive” and “rheological adjuvant” are interchangeable herein. Optional additives are preferably selected from the group consisting of flow control agents, surface-active agents such as surfactants, wetting and dispersing agents, and also thickening agents, thixotropic agents, plasticizers, lubricating and antiblocking additives, and mixtures thereof. These terms are likewise known to the person skilled in the art, for example, from Roempp Lexikon, "Lacke und Druckfarben", Thieme Verlag, 1998. A flow control agent is a component that helps the coating material flow evenly to form a film by lowering the viscosity and/or surface tension. Wetting and dispersing agents are components that lower the surface tension, or in general, the interfacial tension. Lubricating and anti-blocking additives are ingredients that reduce sticking to each other (blocking).

Examples of commercially available additives include Efka® SL 3259, Byk® 377, Tego® Rad 2500, Tego® Rad 2800, Big® 394, Byk-SILCLEAN 3710, Silixan® A250, Novec FC 4430 and Novec FC 4432. A suitable total amount of the at least one additive is, for example, 0.01 to 5% by weight, 0.2 or 0.5 to 3% by weight, based on the total weight of the coating composition (C1a).

In the context of the present invention, additives such as surface agents may include silicone (meth)acrylates. These additives, including silicone (meth)acrylates, at least have a technical effect that not only the additives are included in a small total amount in the coating composition, but also the different chemical functionalities or reactivity of the silicone (meth)acrylate additives are completely different on the coating composition. should not be compared with crosslinkable silicone (meth)acrylate oligomers used as crosslinkable polymers and/or oligomers. Additives comprising silicone (meth)acrylates, for example, only affect the surface energy of the coating composition, and only marginally on the backbone of the (co-)polymerized network formed by the crosslinkable polymer and/or oligomer or reactive diluent. only contribute Unlike additives comprising silicone (meth)acrylates, silicone (meth)acrylate oligomers used as crosslinkable polymers and/or oligomers contain pendant unsaturated groups capable of forming free radicals for crosslinking reactions, reactive diluents together to form a copolymerized elastomeric network of the cured master coating (C1).

Particularly preferably, the components (a), (b), (c) and (d) comprised in the coating composition (C1a) are each different from each other and therefore not identical.

A particularly preferred master coating (C1a) therefore comprises - based on the total weight of the coating composition (C1a) - the following components:

- from 9 to 35% by weight of exactly one silicone (meth)acrylate oligomer comprising on average two unsaturated groups,

- 55 to 83% by weight of a (meth)acrylate derived from hexane diol diacrylate and/or 6-fold ethoxylated trimethylolpropane (ie a compound comprising three structural units of formula (I)) ,

- from 1 to 10% by weight of ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate and/or 1-benzoylcyclohexan-1-ol, and

- 0 or 0.5 to 3% by weight of lubricating and antiblocking additives.

The double bond conversion of the at least partially cured coating (C1) obtained from (C1a) is preferably at least 70%, more preferably at least 75%, even more preferably at least 80%, very preferably at least 85% %, more particularly at least 90%.

The coating composition (C1a) comprises at least one further component (e) different from components (a) to (d), such as, for example, fillers, pigments, thermally activatable initiators such as, for example, potassium peroxo Disulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobisisobutyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl perocto acid or benzopinacol, cumene hydroperoxide, dicumyl peroxide, tert-butyl perbenzoate, silylated pinacol, alkoxyamine, and organic solvents, and also stabilizers. However, preferably, the coating composition (C1a) is free of organic solvents. The coating composition (C1a) comprises at least one in a total amount of 0 to 10% by weight, preferably 0 to 5% by weight, more preferably 0 to 1% by weight, based on the total weight of the coating composition (C1a). component (e).

The coating composition (C1a) may be a solvent-based or solid coating composition. The coating composition (C1a) is preferably a solid coating composition in order to enable rapid curing and to prevent the generation of a solvent which evaporates in a large amount upon curing. Accordingly, the coating composition (C1a) is advantageously less than 10% by weight, preferably less than 5% by weight, more preferably less than 1% by weight, very preferably less than 1% by weight, based on the total weight of the coating composition (C1a). contains solvent in a total amount of 0% by weight or no solvent at all. Accordingly, the coating composition (C1a) advantageously has a solids content of from 75 to 100% by weight, based on the total weight of the coating composition (C1a), as determined at 125°C and 60 min according to DIN EN ISO 3251:2008-06 have content. Furthermore, it comprises advantageously from 90 to 100% by weight, preferably from 95 to 100% by weight, more preferably from 99 to 100% by weight of the compound (a), based on the total weight of the coating composition (C1a), (b), (c) and optionally (d). Most preferably, the coating composition (C1a) consists of compounds (a), (b), (c) and optionally (d).

The coating composition (C1a) is preferably free of thiols and in particular free of trimethylolpropane tris(3-mercaptopropionate).

Coating composition (C2a)

Any kind of coating composition can be used as coating composition (C2a) in step (2-i) or (2-ii) of the process of the present invention. The coating composition (C2a) may be a physically dry, thermally curable, chemically curable and/or radiation-curable coating composition (C2a). The coating composition (C2a) is preferably a chemically curable, thermally curable and/or radiation-curable coating composition, more preferably a radiation-curable coating composition. Accordingly, the at least partial curing according to step (4) is preferably effected by radiation curing. The coating composition (C2a) may be the same as the coating composition (C1a). However, preferably, (C2a) is different from (C1a). (C2a) preferably consists of similar, but not identical to, components (a) to (e) also used in the preparation of (C1a), but the conditions of the quantity associated with (C1a) do not apply to (C2a) you don't have to

Physical drying here refers to forming the coating (C2), preferably by simple evaporation of the solvent(s). Thermal curing here is preferably accompanied by a curing mechanism resulting from temperatures above room temperature (>23° C.). This may be, for example, the formation of radicals or ions, preferably radicals, from an initiator which decomposes at elevated temperature to initiate radical or ionic polymerization. Examples of such thermally activatable initiators are those having a half-life of less than 100 hours at 80°C. Chemical curing is preferably a reaction of at least two different mutually complementary reactive functional groups, for example in a polycondensation manner such as reaction of an -OH group with a -COOH group, or a reaction in a polyaddition manner (NCO group and -OH or reaction of an amino group).

If the coating composition (C2a) is a physically dry, thermally curable and/or chemically curable coating composition, it is prepared using at least one customary polymer known to the person skilled in the art as binder. In the case of thermally or chemically curable coating compositions, such binders preferably have crosslinkable functionalities. Any customary crosslinkable functionalities known to the person skilled in the art are suitable in this regard. More specifically, the crosslinkable functional group is selected from the group consisting of a hydroxyl group, an amino group, a carboxylic acid group, a thiol group, an isocyanate, a polyisocyanate and an epoxide. Preferably the polymer is curable or crosslinkable exothermically or endothermally, preferably in a temperature range from -20°C to 250°C, or from 18°C to 200°C. Polyurethane, polyether, polyester, polyamide, polyurea, polyvinyl chloride, polystyrene, polycarbonate, poly(meth)acrylate, epoxy resin, phenol-formaldehyde resin, melamine-formaldehyde resin At least one polymer selected from is particularly suitable as polymer. These polymers may in particular be OH-functional. In this case, they may be encompassed by the generic term “polyol”. Such polyols are, for example, poly(meth)acrylate polyols, polyester polyols, polyether polyols, polyurethane polyols, polyurea polyols, polyester-polyacrylate polyols, polyester-polyurethane polyols, polyurethane-polyacrylics late polyols, polyurethane-modified alkyd resins, fatty acid-modified polyester-polyurethane polyols, and also mixtures of the specified polyols. Poly(meth)acrylate polyols, polyester polyols and polyether polyols are preferred.

at least one polymer, very preferably at least one corresponding polyurethane and/or at least one corresponding polyurea (for example the so-called "polyaspart acid binders"). Polyaspartic acid binders are components that are converted from the reaction of amino-functional compounds, particularly secondary amines, with isocyanates. If at least one polyurethane is used, particularly suitable ones are prepared by polyaddition reaction between a hydroxyl-containing component such as a polyol and at least one polyisocyanate (aromatic and aliphatic isocyanate, di-, tri- and/or polyisocyanate) possible polyurethane-based resins. Here a stoichiometric conversion of the OH groups of the polyol and the NCO groups of the polyisocyanate is usually required. However, the stoichiometric ratio used may also vary, since the polyisocyanate may be added to the polyol component in an amount such that "over crosslinking" or "under crosslinking" can occur. If epoxy resins, ie epoxide-based resins, are used, suitable ones are epoxide-based resins prepared from glycidyl ethers preferably having terminal epoxide groups and hydroxyl groups in the molecule as functional groups. These are preferably reaction products of bisphenol A with epichlorohydrin and/or bisphenol F with epichlorohydrin, and mixtures thereof, which are also used in the presence of reactive diluents. Curing or crosslinking of such epoxide-based resins is usually by polymerization of the epoxide groups of the epoxide ring, by polyaddition in the form of an addition reaction of an epoxide group with a stoichiometric amount of another reactive compound as a hardener ( Thus in this case, the presence of 1 equivalent of active hydrogen per epoxide group is required (i.e. 1 H-active equivalent per epoxide equivalent is required for curing), or achieved by polycondensation via epoxide groups and hydroxyl groups. do. Examples of suitable hardeners are polyamines, in particular (hetero)aliphatic, (hetero)aromatic and (hetero)cycloaliphatic polyamines, polyamidoamines, polyaminoamides, and also polycarboxylic acids and their anhydrides.

The concept of "radiation curing" has already been described above in relation to the coating composition (C1a), reference is made explicitly to that paragraph.

The coating composition (C2a) can be cured using a radiation source, preferably UV radiation. Accordingly, preferably (C2a) is a UV radiation-curing coating composition.

Accordingly, a preferred product coating composition (C2a) comprises:

a) at least one compound having on average at least two unsaturated groups,

b) optionally at least one photoinitiator, and

c) optionally at least one additive.

The coating composition (C2a) preferably has on average at least two unsaturated carbon double bonds, more preferably (meth)acrylic groups. For this purpose, the coating composition (C2) comprises any of the crosslinkable polymers and/or oligomers or reactive diluents identified above in relation to (C1a), such as, in particular, polyesters, polyethers, carbonates, epoxides , poly(meth)acrylate, urethane (meth)acrylate, and/or silicone (meth)acrylate oligomer and/or at least one unsaturated polyester resin and/or monofunctional, difunctional and/or trifunctional (meth) ) may contain acrylic acid esters.

Upon curing by means of visible light to (N)IR light and/or UV light, the coating composition (C2a) preferably comprises at least one photoinitiator capable of being decomposed into radicals by light of the irradiated wavelength, which in turn A radical may initiate radical polymerization. In contrast, in the case of curing by means of electron radiation, the presence of such a photoinitiator is not required. As photoinitiator, it is possible to use the same components as those specified above with respect to the photoinitiator of the coating composition (C1a) in the same amount.

The coating composition (C2a) may comprise at least one further additive. In this case, it is possible to use the same components as identified above as additives or further component (e) of the coating composition (C1a) in the same amount.

The coating composition used as the coating composition (C2a) is more preferably one having a (meth)acrylic group. Preferably, this coating composition (C2a) comprises at least one urethane (meth)acrylate. Furthermore, preferably, it comprises at least one photoinitiator.

The coating composition (C2a) may be a solvent-based or solid coating composition. In order to enable rapid curing and to prevent the generation of a solvent evaporating in a large amount upon curing, the coating composition (C2a) is preferably a solid coating composition or a coating composition containing a small amount of solvent. It therefore advantageously has a solids content of from 75 to 100% by weight, based on the total weight of the coating composition (C2a), as determined at 125°C and 60 min according to DIN EN ISO 3251:2008-06. Furthermore, it is advantageously from 90 to 100% by weight, preferably from 95 to 100% by weight, more preferably from 99 to 100% by weight of the compound (a) and the total amount of optional compounds (b) and (c).

Complex of the present invention (S1C1)

A further subject of the invention is a composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1), wherein the coating (C1) comprises at least a part of the surface of the substrate (S1) obtainable by at least partially curing by means of radiation curing a coating composition (C1a) applied to and at least partially embossed, wherein the coating composition (C1a) is a radiation-curable coating composition comprising:

(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight or 85% by weight, preferably 50 to 95% by weight or 85% by weight or 83% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

complex (S1C1).

Preferably, all components (a), (b), (c) and (d) are each different from one another.

All preferred embodiments described above with respect to the process of the invention, in particular with respect to the coating composition (C1a) and the substrate (S1) and also the coating (C1) used therein, are also preferred for the composite (S1C1) of the invention embodiment.

The complex (S1C1) of the invention is preferably obtainable by carrying out the above-described process steps (6) to (9) of the process of the invention. The substrate S1 is advantageously a film web, preferably a moving film web, more preferably a moving continuous film web.

Use according to the invention

A further subject of the invention is an embossing tool (E2) for transferring an embossing structure to at least a part of the surface of the coating composition (C2a) or to at least part of the surface of the coating composition (C2a) applied at least partially to the substrate (S2) use of the composite (S1C1) of the present invention as an embossing mold (e2) of

All preferred embodiments described above in relation to the process of the invention and the complex of the invention (S1C1) are also preferred embodiments for the above-mentioned uses of the complex of the invention (S1C1).

The coating composition (C2a) here is preferably a radiation-curable coating composition.

The invention is described in particular by the following embodiments:

Embodiment 1: A method for transferring an embossed structure to at least a portion of a surface of a coating composition (C2a) using a composite (S1C1), comprising at least steps (1), (2-i) and (3-i) or (2) -ii) and (3-ii) and also at least step (4) and optionally step (5-i) or (5-ii), in particular the following steps:

(1) providing a composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1);

and

(2-i) applying at least one coating composition (C2a) to at least a portion of the surface of the substrate (S2) to provide a composite (S2C2a);

(3-i) at least partially embossing the coating composition (C2a) of the composite (S2C2a) using the composite (S1C1) to provide the composite (S1C1C2aS2);

or

(2-ii) at least one coating composition (C2a) is applied to at least a portion of the at least partially embossed and at least partially cured surface of the composite (S1C1), and the coating composition (C2a) using the composite (S1C1) at least partially embossing to provide a composite (S1C1C2a);

(3-ii) optionally applying the substrate (S2) to at least a portion of the surface formed by the coating composition (C2a) of the composite (S1C1C2a) to provide a composite (S1C1C2aS2);

and

(4) at least partially curing the at least partially embossed coating composition (C2a), optionally applied to the substrate (S2), in contact with the composite (S1C1) throughout the duration of the at least partial cure to make the composite providing (S1C1C2) or (S1C1C2S2);

and

(5-i) optionally, removing the complex (C2S2) in the complex (S1C1C2S2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);

or

(5-ii) optionally, removing the coating (C2) in the complex (S1C1C2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);

wherein the coating used to prepare the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-i) or step (5-ii) Composition (C1a) is a radiation-curable coating composition comprising:

(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

Way.

Embodiment 2: A method for transferring an embossed structure to at least a portion of a surface of a coating composition (C2a) using a composite (S1C1), comprising at least steps (1), (2-i) and (3-i) and also at least Step (4) and optionally step (5-i), specifically comprising the following steps:

(1) providing a composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1);

(2-i) applying at least one coating composition (C2a) to at least a portion of the surface of the substrate (S2) to provide a composite (S2C2a);

(3-i) at least partially embossing the coating composition (C2a) of the composite (S2C2a) using the composite (S1C1) to provide the composite (S1C1C2aS2);

(4) at least partially curing the at least partially embossed coating composition (C2a), optionally applied to the substrate (S2), in contact with the composite (S1C1) throughout the duration of the at least partial cure to make the composite providing (S1C1C2S2);

(5-i) optionally, removing the complex (C2S2) in the complex (S1C1C2S2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);

wherein the coating composition (C1a) used to prepare the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-i) comprises A radiation-curable coating composition comprising:

(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

Way.

Embodiment 3: A method of transferring an embossed structure to at least a portion of a surface of a coating composition (C2a) using a composite (S1C1), comprising at least steps (1), (2-ii) and also at least step (4) and optionally as step (5-ii), specifically comprising the following steps:

(1) providing a composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1);

(2-ii) at least one coating composition (C2a) is applied to at least a portion of the at least partially embossed and at least partially cured surface of the composite (S1C1), and the coating composition (C2a) using the composite (S1C1) at least partially embossing to provide a composite (S1C1C2a);

(4) at least partially curing the at least partially embossed coating composition (C2a) in contact with the composite (S1C1) throughout the duration of at least partial curing to provide a composite (S1C1C2);

and

(5-ii) optionally, removing the coating (C2) in the complex (S1C1C2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);

wherein the coating composition (C1a) used to prepare the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-ii) comprises A radiation-curable coating composition comprising:

(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

Way.

Embodiment 4: A method for transferring an embossed structure to at least a portion of a surface of a coating composition (C2a) using a composite (S1C1), comprising at least steps (1), (2-ii) and (3-ii) and also at least Step (4) and optionally step (5-ii), specifically comprising:

(1) providing a composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1);

(2-ii) at least one coating composition (C2a) is applied to at least a portion of the at least partially embossed and at least partially cured surface of the composite (S1C1), and the coating composition (C2a) using the composite (S1C1) at least partially embossing to provide a composite (S1C1C2a);

(3-ii) applying the substrate (S2) to at least a portion of the surface formed by the coating composition (C2a) of the composite (S1C1C2a) to provide a composite (S1C1C2aS2);

(4) at least partially curing the at least partially embossed coating composition (C2a), applied to the substrate (S2), in contact with the composite (S1C1) throughout the duration of the at least partial cure to obtain a composite (S1C1C2S2) providing;

(5-i) optionally, removing the complex (C2S2) in the complex (S1C1C2S2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);

wherein the coating composition (C1a) used to prepare the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-i) comprises A radiation-curable coating composition comprising:

(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

Way.

Embodiment 5: The composition according to any one of embodiments 1 to 4, wherein the at least one coating composition (C2a) in steps (2-i) and (2-ii) is at least 0.5 μm, preferably at least 1 μm, more than preferably applied with a dry layer thickness of at least 5 μm.

Embodiment 6: The embossing structure according to any one of embodiments 1 to 5, wherein the embossed structure to be transferred is preferably in the range from 10 nm to 500 μm, more preferably in the range from 25 nm to 400 μm, very preferably 50 nm structure width in the range from to 250 μm, more particularly in the range from 100 nm to 100 μm, and preferably in the range from 10 nm to 500 μm, more preferably in the range from 25 nm to 400 μm, very preferably from 50 nm to Methods which are microstructures and/or nanostructures having a structure height in the range of 300 μm, more particularly in the range of 100 nm to 200 μm.

Embodiment 7: The method according to any one of embodiments 1 to 6, wherein at least one adhesive is applied to the surface of the substrate (S2) which is not in contact with the coating composition (C2a).

Embodiment 8: The complex (S1C1) provided in step (1) according to any one of embodiments 1 to 7, wherein in step (5-i) the complex (C2S2) is obtained by exfoliation from the complex (S1C1C2S2) additionally restored, or vice versa.

Embodiment 9: The at least partially embossed and at least partially cured coating (C2) in step (5-ii) as a free-standing film by peeling from the composite (S1C1C2) As obtained, the complex (S1C1) provided in step (1) is further restored, or vice versa.

Embodiment 10: The method according to any one of embodiments 1 to 7, wherein the removal from the complex (S1C1) comprises the steps of:

5-i-a) applying at least one adhesive layer (AL) on the surface of the substrate (S2) which is not in contact with the at least partially embossed coating (C2) to provide a composite (S1C1C2S2AL);

5-i-b) optionally, at least partially attaching the complex (S1C1C2S2AL) to the object (O1);

5-i-c) removing, preferably exfoliating, the complex (S1C1) from the complex (C2S2AL) optionally at least partially attached to the object (O1) or vice versa.

Embodiment 11: The method according to any one of embodiments 1 to 7, wherein removing from the complex (S1C1) comprises the steps of:

5-ii-a) applying at least one adhesive layer (AL) on at least a portion of the unstructured surface of the at least partially embossed coating (C2) to provide a composite (S1C1C2AL);

5-ii-b) optionally, at least partially attaching the complex (S1C1C2AL) to the object (O1);

5-ii-c) removing, preferably exfoliating, the complex (S1C1) from the complex (C2S2AL) optionally at least partially attached to the object (O1) or vice versa.

Embodiment 12: The complex (S1C1) according to any one of embodiments 1 to 11, wherein the complex (S1C1) provided in step (1) is coated in step (2-i) and in steps (2-ii) and (3-ii) ( used as an embossing mold (e2) of an embossing tool (E2) for transferring the embossing structure of C1) to the coating composition (C2a) as an embossing structure,

An at least partially embossed and at least partially cured coating (C2), wherein the mirror image of the structured surface of the coating (C1) of the composite (S1C1) used here as the embossing mold (e2) is optionally applied to the substrate (S2) ) that is embossed with the surface of

Way.

Embodiment 13: The method according to any one of embodiments 1 to 12, wherein the substrate (S1) is a film web, preferably a moving film web or a continuous film web, more preferably a moving continuous film web.

Embodiment 14: The method according to any one of embodiments 1 to 13, wherein the substrate (S2) is a film web, preferably a moving film web, more preferably a moving continuous film web.

Embodiment 15: The method according to any one of embodiments 1 to 14, wherein the complex (S1C1) used in step (2-i), and in steps (2-ii) and (3-ii) is reusable, the step of the method wherein (5-i) or (5-ii) is performed, it can be used repeatedly to transfer at least one embossing structure.

Embodiment 16: The method according to any one of embodiments 1 to 15, wherein during the execution of step (3-i), in step (3-i) the composite (S1C1) is passed through a first roll serving as an embossing tool (E2). being guided, the composite (S2C2a) being guided through a second roll disposed opposite the first roll and counter-rotating or co-rotating therewith,

During the execution of step (3-ii), the composite (S1C1C2a) in step (3-ii) is guided through a first roll serving as an embossing tool (E2), and the substrate (S2) used in step (3-ii) ) is directed through a second roll disposed opposite the first roll and counter-rotating or co-rotating therewith.

Way.

Embodiment 17: The method of embodiment 16, wherein the at least partial embossing of step (3-i) is carried out at the level of a roll nip formed by two counter-rotating or co-rotating mutually opposing rolls , wherein the at least partially embossed coating (C1) of the composite (S1C1) faces the coating composition (C2a) of the composite (S2C2a),

The at least partial embossing of step (3-ii) is carried out at the level of a roll nip formed by two counter-rotating or co-rotating mutually opposing rolls, wherein the coating composition of the composite (S1C1C2a) ( that C2a) faces the substrate S2

Way.

Embodiment 18: The method according to any one of embodiments 1 to 17, wherein the complex (S1C1) provided in step (1) is obtainable by at least the following steps:

(6) applying the radiation-curable coating composition (C1a) to at least a portion of the surface of the substrate (S1) to provide a composite (S1C1a);

(7) at least partially embossing the coating composition (C1a) at least partially applied to the surface of the substrate (S1) by means of at least one embossing tool (E1) comprising at least one embossing mold (e1);

(8) contacting the at least partially embossed coating composition (C1a), at least partially applied to the substrate (S1), with at least one embossing mold (e1) of the embossing tool (E1) throughout the duration of at least partial curing at least partially curing it in an intact state;

(9) removing the composite (S1C1) from the embossing mold (e1) of the embossing tool (E1) or vice versa to provide an at least partially embossed and at least partially cured composite (S1C1).

Embodiment 19: The method according to embodiment 18, wherein in step (6) the at least one coating composition (C1a) is applied with a dry layer thickness of at least 0.5 μm, preferably at least 1 μm, more preferably at least 5 μm. how to be.

Embodiment 20: The composition according to any one of embodiments 1 to 19, wherein the coating composition (C1a) comprises from 5 to 45% by weight, preferably from 8 to 40% by weight, based on the total weight of the coating composition (C1a), more preferably at least one crosslinkable polymer and/or oligomer in a total amount of 9 to 35% by weight.

Embodiment 21: the coating composition (C1a) according to any one of embodiments 1 to 20, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a), at least 25% by weight , preferably at least 50% by weight, more preferably at least 90% by weight, very preferably 100% by weight of at least one silicone (meth)acrylate oligomer, preferably exactly one silicone (meth)acrylic a rate oligomer, more preferably exactly one silicone (meth)acrylate oligomer comprising on average 2 to 3 unsaturated groups.

Embodiment 22: The composition according to any one of embodiments 1 to 21, wherein the coating composition (C1a) comprises from 5 to 45% by weight, preferably from 8 to 40% by weight, based on the total weight of the coating composition (C1a), more preferably comprising at least one crosslinkable polymer and/or oligomer selected from the group consisting of: i) at least one silicone (meth)acrylate oligomer, preferably in a total amount of 9 to 35% by weight is exactly one silicone (meth)acrylate oligomer, very preferably exactly one silicone (meth)acrylate oligomer comprising on average 2 to 3 unsaturated groups, and ii) a (meth)acrylated oligomer or polymer compound, Urethane (meth)acrylate, vinyl (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, poly(meth)acrylate, polyether (meth)acrylate, olefin (meth)acrylate , (meth)acrylated oils, and mixtures thereof, preferably other crosslinkable polymers and/or oligomers selected from urethane (meth)acrylate oligomers.

Embodiment 23: The coating composition (C1a) according to any one of embodiments 1 to 22, wherein the coating composition (C1a) is a reactive diluent free-radically polymerizable monomer, preferably an ethylenically-unsaturated monomer, more preferably a polyfunctional ethylenically unsaturated monomer A method comprising

Embodiment 24: The coating composition (C1a) according to any one of embodiments 1 to 23, wherein the coating composition (C1a) comprises hexane diol diacrylate and at least two structural units of formula (I) which may be different from each other or may be at least partially identical to each other. A method comprising at least one reactive diluent selected from compounds comprising a dog, preferably at least three, more preferably three:

here

The radicals R ¹ are, independently of one another, a C ₂ -C ₈ alkylene group, very preferably a C ₂ alkylene group,

The radicals R ² are, independently of one another, H or methyl,

parameter m independently of one another is an integer in the range from 1 to 15, very preferably from 1 to 4 or from 2 to 4, provided that in at least one of the structural units of formula (I) the parameter m is at least 2, preferably exactly 2 is

Embodiment 25: The method according to embodiment 24, wherein said compound comprises three identical structural units of formula (I) and the parameter m is at least 2, preferably exactly 2.

Embodiment 26: The compound of any one of embodiments 24 or 25, wherein the compound of at least one reactive diluent comprises at least two structural units of formula (I), which total from 4-fold to 20-fold or 4-fold neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol, preferably ethoxylated, propoxylated or ethoxylated and propoxylated, very preferably ethoxylated with a to 12-fold alkoxylation (meth)acrylates of sylated neopentyl glycol, trimethylolpropane, trimethylolethane or pentaerythritol, most preferably (meth)acrylates derived from alkoxylated trimethylolpropane.

Embodiment 27: The composition according to any one of embodiments 1 to 6, wherein the coating composition (C1a) comprises 40 to 95% by weight, preferably 50 to 85% by weight, based on the total weight of the coating composition (C1a), more preferably comprising (meth)acrylate derived from at least one reactive diluent, preferably hexane diol diacrylate and/or 6-fold ethoxylated trimethylolpropane in a total amount of 55 to 83% by weight how to be.

Embodiment 28: The composition according to any one of embodiments 1 to 27, wherein the coating composition (C1a) comprises from 0.01 to 15% by weight, preferably from 0.5 to 10% by weight, based on the total weight of the coating composition (C1a), more preferably comprising at least one photoinitiator in a total amount of 1 to 8% by weight.

Embodiment 29: The photoinitiator according to any one of embodiments 1 to 28, wherein the photoinitiator included in the coating composition (C1a) is phosphine oxides, including (alkyl)-benzoylphenylphosphine oxides, benzophenones, α-hydroxy Alkyl aryl ketones, thioxanthones, anthraquinones, acetophenones, benzoins and benzoin ethers, ketals, imidazoles or phenylglyoxylic acids and mixtures thereof, preferably diphenyl (2,4, 6-Trimethylbenzoyl)phosphine oxide, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, benzophenone, 1-benzoyl cyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof.

Embodiment 30: The coating composition (C1a) according to any one of embodiments 1 to 29, based on the total weight of the coating composition (C1a), 0.01 to 5% by weight, preferably 0.2 or 0.5 to 5% by weight %, more preferably 0.5 to 3% by weight of the at least one additive.

Embodiment 31: The composition according to any one of embodiments 1 to 30, wherein the coating composition (C1a) is less than 10% by weight, preferably less than 5% by weight, more preferably less than 5% by weight, based on the total weight of the coating composition (C1a). preferably comprising an organic solvent in a total amount of less than 1% by weight, and very preferably no organic solvent at all.

Embodiment 32: The composition according to any one of embodiments 1 to 30, wherein the coating composition (C1a) comprises from 90 to 100% by weight, preferably from 95 to 100% by weight, based on the total weight of the coating composition (C1a), more preferably comprising components (a), (b), (c) and optionally (d) in a total amount of 99 to 100% by weight.

Embodiment 33: A composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1), wherein the coating (C1) is applied to at least a portion of the surface of the substrate (S1) and obtainable by at least partially curing the at least partially embossed coating composition (C1a) by means of radiation curing, wherein the coating composition (C1a) is a radiation-curable coating composition comprising:

(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,

(b) 40 to 95% by weight of at least one reactive diluent;

(c) 0.01 to 15% by weight of at least one photoinitiator, and

(d) 0 to 5% by weight of at least one additive;

wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a) and (ii) the amount of components present in the coating composition (C1a) The total amount of all components adds up to 100% by weight;

wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight

complex (S1C1).

Embodiment 34: The complex (S1C1) according to embodiment 33, wherein the complex (S1C1) is obtainable by carrying out the method steps (6) to (9) described in embodiment 18 or 19.

Embodiment 35 Composite (S1C1) according to embodiment 33 or 34, wherein the substrate (S1) is a film web, preferably a moving film web, more preferably a moving continuous film web.

Embodiment 36: Embossing mold of an embossing tool (E2) for transferring an embossing structure to at least a portion of the surface of the coating composition (C2a) or to at least a portion of the surface of the coating composition (C2a) applied at least partially to the substrate (S2) Use of the complex (S1C1) according to any one of embodiments 33 to 35 as (e2).

Embodiment 37: The composition according to any one of embodiments 1 to 5, wherein the radiation-curable coating composition (C1a) comprises from 50 to 95% by weight, or from 50 to 85% by weight, based on the total weight of the coating composition (C1a). , or 50 to 83% by weight of at least one reactive diluent.

Embodiment 38: The composition of any one of embodiments 33 to 36, wherein the radiation-curable coating composition (C1a) comprises from 50 to 95% by weight, or from 50 to 85% by weight, based on the total weight of the coating composition (C1a). , or 50 to 83% by weight of at least one reactive diluent.

How to decide

1 . Determination of mold filling

Mold filling is determined by commercial scanning electron microscopy (SEM). Surfaces of defined lattice structures of different master films (S1C1), for example after embossing, by SEM, with features of, for example, a structure width in the range of 10 nm to 1000 μm and a structure depth in the range of 1 nm to 1000 μm It is possible to compare the topography correspondingly. Mold filling is considered complete if a pointed feature, such as the tip of a triangular-shaped structure, is fully replicated. A comparison of the surface topography of the different master films (S1C1) as well as the mold filling can also be compared.

2. Determination of flow time

The flow time is determined according to DIN EN ISO 2431 (date: March 2012). The method involves determining the flow time by means of a 4 mm flowmeter cup (No. 4), 5 mm flowmeter cup (No. 5) or 6 mm flowmeter cup (No. 6) at room temperature (20° C.) .

40 or 50 to 100 s measured with a 4 mm flowmeter cup, 30 to 100 s measured with a 5 mm flowmeter cup, and 30 to 200 s, preferably 30 to 150 s, measured with a 6 mm flowmeter cup, More preferably a flow time in the range of 30 to 115 s is considered acceptable. Therefore, a coating composition with a flow time of > 200 s into a 6 mm rheometer cup is considered unfavorable, as the coating composition does not spread quickly enough to a uniform layer thickness over the entire width of the substrate or composite, resulting in a molded mold. This is because the quality of filling and duplication will deteriorate, and the risk of air entrainment in the applied coating composition increases as the flow time increases. On the other hand, a flow time of < 40 or 50 s with a 4 mm rheometer cup simply flows off the substrate when the coating composition is applied, for example, in a roll-to-roll (R2R) embossing device, which results in sufficient mold filling and because it does not provide sufficient cohesiveness within the layer to allow sufficient layer thickness to emboss microstructures and nanostructures with transfer quality.

3 . Determination of Adhesion

3.1 cross hatch test

The adhesion is determined by a cross hatch test according to DIN EN ISO 2409 (date: June 2013). With this test, the adhesion of the coating layer under inspection to the substrate is tested by redundancy determination. A cross hatch tester from Byk Gardner with a cut gap of 2 mm is used manually. Then, Tesa tape No. 4651 is pressed over the damaged area and peeled off to remove the delaminated areas. Evaluations are made based on characterization values ranging from 0 (minimal delamination) to 5 (very large delamination). An average value of 3.5 or less is classified as sufficient.

3.2 X-shaped cut (St. Andrew's cross)

Adhesion is determined by a dedicated cross-cut test. In this test, the coating layer is cut in an X shape (length: 10 cm, angle: 45°) by manual scalpel. Then, tesa tape No. 4651 is pressed over the damaged area and peeled off to remove the delaminated areas. If the coating layer does not show visible delamination after cutting and/or peeling of the tape, the adhesion of the coating layer is rated "Pass". If the coating layer shows visible delamination after cutting and/or peeling of the tape, the adhesion of the coating layer is rated "fail".

4 . Determination of replication success rate

The replication success rate is determined by visually identifying the percentage fraction of the area successfully replicated. Here there is a range of areas successfully replicated from 0% to 100%. If less than 100% of the area is replicated, this means that a corresponding fraction of the area could not be removed from the embossing mold, that is to say that the coating C1 in the form S1C1 partially adheres to the embossing mold (e1) of the embossing tool (E1). It means that it remains, or that the coating C2 remains partially adhered to the composite (S1C1) after separation.

5 . Determination of layer thickness distribution

The layer thickness distribution is determined by measuring the layer thickness of the composite S1C1 with the imprinted structure. In other words, the total thickness determined for the laminate S1C1 is the sum of the individual heights of the substrate S1, the remaining layers of the coating C1, and the structures formed inside or outside the coating C1. The thickness is according to procedure 12A of DIN EN ISO 2808 (date: May 2007), minitest by ElectroPhysik in combination with a F1.6 probe (measurement uncertainty: ± (1% + 1 μm)) ( MiniTest)® 2100 microprocessor coating thickness gauge. In the absence of a ferromagnetic substrate, the composite S1C1 was placed on a flat ferromagnetic plate and measurements were performed. Determine the layer thickness at nine predefined points arranged in a 3x3 matrix on a 15 cm x 15 cm patch of S1C1. All measurement points are spaced 5 cm apart from each other, and the first measurement point or starting measurement point is 2.5 cm from the top and 2.5 cm from the left side of the 15 cm x 15 cm patch of S1C1. Accordingly, the second measurement point is located 2.5 cm from the top and 7.5 cm from the left side of the 15 cm x 15 cm patch of S1C1.

6 . Determination of flexibility

The flexibility of each composite (S1C1) was determined by folding the composite by 180°. If no visible cracks and/or damage were observed in the coating (C1) during and/or after folding, the rating is “Pass”. If visible cracks and/or damage are observed in the coating (C1) during and/or after folding, the rating is “fail”.

Examples of the present invention and comparative examples

The following inventive and comparative examples are provided to illustrate the invention, but should not be construed as imposing any limitation.

Unless otherwise indicated, amounts expressed in parts are parts by weight, and amounts expressed in percent are in each case a percentage by weight.

One. Ingredients and Substances Used

Hostaphan® GN CT01B - a commercially available PET film with a layer thickness of 175 μm, chemically treated on both sides to improve the adhesion of the coating.

A commercially available PET film provided by SKC, Korea, having a layer thickness of 125 μm, urethane coated on both sides for improved adhesion to inks and coatings, especially UV curing inks.

Laromer® UA 9033 (L UA 9033) - aliphatic urethane acrylates from BASF SE

Laromer® UA 9089 (L UA 9089) - aliphatic urethane acrylates from BASF SE

Hexanediol Diacrylate (HDDA)

Hydroxypropyl acrylate (HPA)

Sartomer® CN9800 (CN9800) - aliphatic silicone acrylate from Sartomer

Sartomer® 499 (SR 499) - 6-fold ethoxylated TMPTA from Sartomer (trimethylolpropane triacrylate)

Sartomer® SR 344 (Arkema Inc.)-polyethylene glycol (400) diacrylate

Irgacure® 184 (I-184) - photoinitiator commercially available from BASF SE

Irgacure® TPO-L (I-TPO-L) - photoinitiator commercially available from BASF SE

TEGO® Rad 2500 (TR 2500) - Lubricating and anti-blocking additive from Evonik (silicone acrylate)

2. Example

2.1 Preparation of coating compositions according to the invention (C1a) (C1a-1) and the corresponding comparative coating compositions (C1a-2)

A coating composition suitable as a coating composition (C1a) for the preparation of the composite (S1C1) was prepared according to Table 1 below. The flow times found at room temperature (20° C.) range from 26 to 172 s for the preparations of C1a-5 and C1a-9.

Table 1: Coating composition (C1a)

* embodiment of the present invention

as described in item 2. (determination of flow time) of inventive examples C1a-2 to C1a-8 having a total amount of reactive diluent of 40 to 80% by weight, based on the total weight of the coating composition (C1a) The flow time determined by the method as described falls within the acceptable range of 50 s measured with a 4 mm flowmeter cup to 200 s measured with a 6 mm flowmeter cup. Comparative Examples C1a-1 (total amount of reactive diluent 35% by weight), C1a-10 (total amount of reactive diluent 25% by weight) and C1a-11 (total amount of reactive diluent 25% by weight, Example 1 of KR 2009/0068490 A) The flow times of the compositions according to

2.2 Preparation of composites (S1C1) using the coating composition according to the invention (C1a-5) and the comparative coating composition (C1a-9)

According to Table 2 below, a number of different composites (S1C1) are prepared using a roll-to-plate (R2P) embossing machine with an embossing mold (e1) made of nickel which holds the desired phase of the structure to be embossed. Here, the phase of the structure of the embossing mold (e1) corresponds to the phase of the structure to be embossed with the coating composition (C2a) in a subsequent step.

In these examples, an embossing mold (e1) made of nickel having a different original structure, specifically having:

61 μm의 높이 및 130 μm의 주기적 반복을 갖는 마이크로구조 M1 (3차원적 삼각형 구조), 또는

microstructure M1 (three-dimensional triangular structure) with a height of 61 μm and periodic repetition of 130 μm, or

42 μm의 높이를 가지며 구조간 55 μm 이격되어 있는 마이크로구조 M2 (2차원적 삼각형 구조).

Microstructure M2 (two-dimensional triangular structure) with a height of 42 μm and separated by 55 μm between structures.

For this purpose, the coating compositions C1a-5 and C1a-9 described above are respectively applied to the embossing mold (e1) of the embossing tool (E1), and a PET film as substrate (S1) is applied thereto. The film and the resulting laminate with each coating composition are then moved through under a pressing roll, and while the embossing device is still in contact with the coating composition of each laminate, the coating composition is at least partially applied by means of a UV-LED lamp. hardened with Then, the at least partially cured coating, having an inverted structure as opposed to the embossing mold (e1), is separated from the embossing apparatus together with the film to provide a structured film (master film) as a composite (S1C1). The master film is then post-exposed to a UVA lamp. The symbol "-" in the table indicates that no special post-cure was performed.

Table 2: Manufacturing parameters

Master films A and B with microstructure M1 were used to determine mold fill quality, adhesion, and replication success rate - see section 2.3.1 - also for the preparation of transfer films as described in items 2.4 to 2.5.2 below and thereto used for inspection. Master films C, D, E and F with microstructure M2 were used for the determination of layer thickness uniformity as described in Section 2.3.2 below. To prepare these master films, coating compositions (C1a-5) and (C1a-9) are used, correspondingly coatings (C1) derived from coating compositions (C1a-5) or (C1a-9) respectively ( C1-5) or (C1-9), and a composite (S1C1) having a microstructure M1 or M2 as the embossed structure is obtained.

In another series of experiments, a composite (S1C1) was prepared according to the manufacturing parameters of "Master Film C" as shown in Table 2, wherein the coating composition (C1a-5) was each prepared according to the coating composition as shown in Table 1 ( Substituted with one of C1a-1) to (C1a-8), (C1a-10) or (C1a-11) to provide master films G to P.

Master films G to P prepared from the coating compositions (C1a-1) to (C1a-8), (C1a-10) or (C1a-11) all presented acceptable layer thicknesses in the range of 203 to 225 μm. The flexibility of the master films G to O, as determined according to the method described in item 6. above, after 7 days of manufacture was "Pass". Only the flexibility of the master film P made from the comparative coating composition (C1a-11) was "failed". Moreover, observation of master films G to P with an Olympus SZX12 stereo microscope revealed unacceptable amounts of air entrainment in the case of master films P prepared from comparative coating compositions (C1a-11).

2.3 Inspection for Master Film (S1C1)

2.3.1 Determination of adhesion and mold filling.

Table 3 below summarizes the tests performed on master films A and B. Each test was performed according to the method described above.

Table 3:

The data in Table 3 show that the excellent adhesion of the master film A of the present invention (cross hatch test and X-cut test), the insufficient adhesion achieved with the comparative master film B (cross hatch test, it was evaluated as having a rating of 5, Negative in the X-cut test) compared to present. If the adhesion of the master coating (C1) to the substrate (S1), in these examples, of the coating compositions (C1-5) and (C1-9) to the PET film, is insufficient, the coating composition (C1a) and also the subsequent In both cases, problems may arise during the embossing of the coating composition (C2a) when the master film is used as the embossing mold (e2).

The replication success rate of master film A remained as good as that of master film B (Table 3, replication success rate). Thus, even with the coating composition usable according to the invention, no residue was left on the embossing mold (e1).

The mold filling of the master films A and B, as described above, was visually inspected for triangular features embossed by the embossing mold (e1) of the embossing tool (E1) with the coating composition (C1a) applied to the substrate (S1) and its It was determined by comparing the SEM images (FIG. 3). Comparison of SEM images of master films A and B reveals a complete and comparable transfer from the embossing mold to the coating composition (C1a) of structures including pointed details such as corners and triangular features. As such, the introduction of a large amount of silicone (meth)acrylate oligomer into the coating composition of (C1a) according to the present invention can be expected due to the different surface tensions of the coating compositions (C1a-5) and (C1a-9). It did not cause any deterioration in mold filling quality. Thus, complete and comparable filling of the inverted features of the mold was observed in both coating compositions C1a-1 and C1a-2.

In summary, it can be said that only Master Film A gave excellent results with respect to all properties tested (adhesion, mold filling, and replication success rate).

2.3.2 Determination of layer thickness uniformity

Table 4 below summarizes the tests performed on master films C, D, E and F. Each test was performed according to the method described above. In this series of experiments, the application pressure (3.3 bar) and slot size (3.28 mm) of the coater for applying the coating composition were the same.

Table 4:

The data in Table 4 show that the maximum difference (the amount of change from the minimum layer thickness (S1C1) to the maximum layer thickness (S1C1)) in the layer thicknesses determined for the master films C and E used according to the invention at two process rates is a comparative master film We present a significant decrease compared to D and F, which is also reflected by the much smaller standard deviation. Moreover, not only the layer thickness of the applied coating composition is much more uniform, but also the average layer thickness itself could be increased.

If the layer thickness of the master coating (C1a) is too non-uniform over the width of the substrate (S1), problems may arise both during embossing of the coating composition (C1a) and also subsequently of the coating composition (C2a). The quality with which the phase of the structure is reproduced from the embossing mold (e1) of the embossing tool (E1) is generally improved, especially in larger dimensions, with a more uniform layer thickness of the coating composition (C1a), which is This is because the pressure applied to imprint the original features of the mold (e1) with the coating composition (C1a) is evenly distributed, enabling equal imprinting over the entire width of the embossing tool. Thus, a uniform layer thickness of the coating composition (C1a) will result in a better quality of reproduction of the features of the embossing mold (e1) in the coating (C1) with a uniform residual layer over the entire or almost the entire width of the film. As a result, in the case of using the composite (S1C1) as the embossing mold itself, for example as the embossing mold (e2), a uniform layer thickness of the coating (C1) is achieved so that the pressure applied to the composite (S1C1) is also in this case the overall composite ( improved transfer of the embossed structure into the coating composition (C2a), as it is more evenly distributed over S1C1), the better replication quality and reproducibility of the embossed structure in the coating composition (C2a) allows for greater transfer will make

In summary, it can be said that the uniformity of the layer thickness of the master films C and E is greatly improved compared with the master films D and F.

2.4 Preparation of transfer film (S1C1C2):

The obtained master films (S1C1), each having the structure M1, were then respectively used in a roll-to-plate (R2P) embossing apparatus, and the coating composition (C2a) was applied to the structured surface of each master film with a dry layer of 40 μm applied in thickness. In order to protect the coating composition (C2a) from oxygen and mechanical influences, the master film and the laminate resulting from the coating composition (C2a) are temporarily lined with a TAC film. The finally obtained laminate comprising the master film (S1C1), the coating composition (C2a) applied thereto, and the TAC film applied to the coating composition (C2a) is then subjected to at least a coating composition (C2a) by means of a UV-LED lamp. In a simultaneous process with partial curing, it is moved through under a pressing roll (applied pressure 6 bar). The lamp used in this case is a 365 nm, 6 W UV-LED lamp from Easytec (100% lamp output, 2 m/min, 2 passes). In this way, after removal of the protective TAC film, a composite (S1C1C2-1) is obtained from the master film A and a composite (S1C1C2-2) is obtained from the master film B.

The coating composition (C2a) used is a commercial radiation-curing coating composition comprising at least one urethane acrylate, at least one photoinitiator and also commercial additives.

2.5 Test for complex (S1C1C2)

2.5.1 i) the separation behavior as a function of time between the preparation of the composite (S1C1) and the application of the coating composition (C2a) and ii) the separation behavior as a function of time between the application and separation of the coating composition (C2a) to the composite (S1C1) .

Replica of the separation behavior between the structured master film (S1C1) and the resulting coating (C2) as a function of aging of the master film (S1C1), according to the specific master film (S1C1) used for embossing in Table 5 below. Inspection results indicated by quality are summarized. The coating (C2) is removed by peeling from the composite (S1C1). The symbol "-" in the table indicates that no special inspection was performed.

Table 5: Separation behavior of the coating composition (C2) from the master film (S1C1)

In the case of using the master film B, if the coating composition (C2a) is applied and separated immediately after curing 5 days after the preparation of the master film (S1C1) from the coating composition (C1a-9), the master film (S1C1) and the coating ( The replication success rate upon isolation of C2) is much lower than <100%, even 0%. Accordingly, most of the coating (C2) could not be separated or removed from the coating (C1) of the associated master film B without destruction of the coating (C2) or the master film B. As shown in Table 2 above, the master film "P" prepared from the comparative coating composition (C1a-11) still showed tack after curing, so that these master films stuck to each other during storage, immediately after curing and after 1 day from curing. This resulted in a poor separation behavior of 0% from the coating (C2). In contrast, in the case of using the master film A to be inspected, the elapsed time between preparation of the master film and application of the coating composition (C2a) or the elapsed time after embossing and curing of the coating composition (C2a) applied to the master film (S1C1) Regardless, a replication success rate of 100% or nearly 100% (97%) is achieved upon isolation. In other words, the use of master film A provides a very high replication success rate (as an indicator for the separation behavior) irrespective of the aging of the master film itself, even in a laminate composed of the master film (S1C1) and the coating (C2) (S1C1C2). ) can be stored or transported. Thus, the master film A, compared to the master film B, directly applies the coating composition (C2a) to the master film, after a few days, or even applies the coating composition (C2a), and applies the coating (C2) to the master film It made it possible to store it together with the master film (S1C1) until separation from (S1C1), thus protecting the imprinted structure of the composite (S1C1), and upon clean release from the residue-free composite (S1C1). This makes it possible to improve the reusability of the composite (S1C1) as an embossing mold and to obtain the embossed coating (C2) as a self-supporting film. 9 days old master film prepared from the coating compositions (C1a-1) to (C1a-8) and (C1a-10), showing a separation behavior of 100% of the coating (C2) immediately after curing and after 1 day from curing Similar descriptions are made for G to O.

2.5.2 Mold filling

The quality of the mold filling of the coating composition (C2a) into the master films A and B usable as embossing molds was visually inspected and the SEM image of the triangular features transferred to the coating composition (C2a) by embossing as described above, as described above. It was determined by comparison, where the same coating composition (C2a) was applied 11 days after preparation of each master foil A or B, and separation was carried out immediately after curing ( FIG. 4 ). Comparison of the SEM images of the embossed and cured coating (C2) after separation from master films A and B shows that again in this case the coating composition (C2a) from master films A and B of structures including sharp details such as corners and triangular features ) to present a complete and similar transcription. In Fig. 4, the coating (C2) derived after separation from the master film A according to the invention is denoted as coating C2-1. Correspondingly, the coating (C2) derived after separation from the master film B is designated as coating C2-2. As such, the introduction of a large amount of silicone (meth)acrylate oligomer into the coating composition of (C1a) according to the present invention is different compared to the surface tension of the coating composition (C2a) in the coating compositions (C1-5) and (C1) -9) did not result in any reduction in mold filling or deterioration in mold filling quality that could be expected due to the surface energy of -9). Thus, a complete and comparable transfer of the original features of the master films A and B comprising the coating compositions (C1a-5) and (C1a-9) was observed.

Claims (18)

A method for transferring an embossed structure to at least a portion of a surface of a coating composition (C2a) using a composite (S1C1), comprising at least steps (1), (2-i) and (3-i) or (2-ii) and (3-ii) and also at least step (4) and optionally step (5-i) or (5-ii), in particular the following steps:
(1) providing a composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1);
and
(2-i) applying at least one coating composition (C2a) to at least a portion of the surface of the substrate (S2) to provide a composite (S2C2a);
(3-i) at least partially embossing the coating composition (C2a) of the composite (S2C2a) using the composite (S1C1) to provide the composite (S1C1C2aS2);
or
(2-ii) at least one coating composition (C2a) is applied to at least a portion of the at least partially embossed and at least partially cured surface of the composite (S1C1), and the coating composition (C2a) using the composite (S1C1) at least partially embossing to provide a composite (S1C1C2a);
(3-ii) optionally applying the substrate (S2) to at least a portion of the surface formed by the coating composition (C2a) of the composite (S1C1C2a) to provide a composite (S1C1C2aS2);
and
(4) at least partially curing the at least partially embossed coating composition (C2a), optionally applied to the substrate (S2), in contact with the composite (S1C1) throughout the duration of the at least partial cure to make the composite providing (S1C1C2) or (S1C1C2S2);
and
(5-i) optionally, removing the complex (C2S2) in the complex (S1C1C2S2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);
or
(5-ii) optionally, removing the coating (C2) in the complex (S1C1C2) from the complex (S1C1) to restore the complex (S1C1) provided in step (1);
wherein the coating is used to prepare the at least partially embossed and at least partially cured coating (C1) of the composite (S1C1) used in step (1) and restored in step (5-i) or step (5-ii) Composition (C1a) is a radiation-curable coating composition comprising:
(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,
(b) 40 to 95% by weight of at least one reactive diluent;
(c) 0.01 to 15% by weight of at least one photoinitiator, and
(d) 0 to 5% by weight of at least one additive;
wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;
wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight
Way. 2 . The radiation-curable coating composition (C1a) according to claim 1 , wherein at least 50 to 95% by weight, alternatively 50 to 85% by weight, alternatively 50 to 83% by weight, based on the total weight of the coating composition (C1a). and one reactive diluent. 3. The embossing structure to be transferred according to claim 1 or 2, preferably in the range from 10 nm to 500 μm, more preferably in the range from 25 nm to 400 μm, very preferably in the range from 50 nm to 250 μm. , more particularly a structure width in the range from 100 nm to 100 μm, and preferably in the range from 10 nm to 500 μm, more preferably in the range from 25 nm to 400 μm, very preferably in the range from 50 nm to 300 μm, more particularly microstructures and/or nanostructures having a structure height in the range from 100 nm to 200 μm. The method according to claim 1 , wherein at least one adhesive is applied to the other surface of the substrate (S2) which is not coated with the coating composition (C2a). 5. The method according to any one of claims 1 to 4, wherein the removal from the complex (S1C1) comprises the steps of:
5-ia) applying at least one adhesive layer (AL) on the surface of the substrate (S2) which is not in contact with the at least partially embossed coating (C2) to provide a composite (S1C1C2S2AL);
5-ib) optionally, at least partially attaching the complex (S1C1C2S2AL) to the object (O1);
5-ic) removing, preferably exfoliating, the composite (S1C1) from the composite (C2S2AL) optionally at least partially attached to the object (O1) or vice versa;
or
5-ii-a) applying at least one adhesive layer (AL) on at least a portion of the unstructured surface of the at least partially embossed coating (C2) to provide a composite (S1C1C2AL);
5-ii-b) optionally, at least partially attaching the complex (S1C1C2AL) to the object (O1);
5-ii-c) removing, preferably exfoliating, the complex (S1C1) from the complex (C2S2AL) optionally at least partially attached to the object (O1) or vice versa. 6. The coating (C1) according to any one of the preceding claims, wherein the complex (S1C1) provided in step (1) is coated (C1) in step (3-i) and in steps (2-ii) and (3-ii). ) as an embossing mold (e2) of an embossing tool (E2) for transferring the embossed structure of the coating composition (C2a) as an embossing structure,
An at least partially embossed and at least partially cured coating (C2), wherein the mirror image of the structured surface of the coating (C1) of the composite (S1C1) used here as the embossing mold (e2) is optionally applied to the substrate (S2) ) that is embossed with the surface of
Way. 7. The substrate (S2) according to any one of the preceding claims, wherein the substrate (S1) is a film web, preferably a moving film web or a continuous film web, more preferably a moving continuous film web, and/or the substrate (S2). ) is a film web, preferably a moving film web, more preferably a moving continuous film web. 8. The method according to any one of claims 1 to 7, wherein the complex (S1C1) used in step (3-i), and steps (2-ii) and (3-ii) is reusable, Where 5-i) or (5-ii) is performed, the method may be used repeatedly to transfer at least one embossing structure. 9. The process according to any one of claims 1 to 8, wherein the complex (S1C1) provided in step (1) is obtainable by at least the following steps:
(6) applying the radiation-curable coating composition (C1a) to at least a portion of the surface of the substrate (S1) to provide a composite (S1C1a);
(7) at least partially embossing the coating composition (C1a) at least partially applied to the surface of the substrate (S1) by means of at least one embossing tool (E1) comprising at least one embossing mold (e1);
(8) contacting the at least partially embossed coating composition (C1a), at least partially applied to the substrate (S1), with at least one embossing mold (e1) of the embossing tool (E1) throughout the duration of at least partial curing at least partially curing it in an intact state;
(9) removing the composite (S1C1) from the embossing mold (e1) of the embossing tool (E1) or vice versa to provide an at least partially embossed and at least partially cured composite (S1C1). 10. The composition according to any one of the preceding claims, wherein the coating composition (C1a) comprises at least 25% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a), Preferably at least one silicone (meth)acrylate oligomer, preferably exactly one silicone (meth)acrylate in a total amount of at least 50% by weight, more preferably at least 90% by weight, very preferably 100% by weight oligomers, more preferably exactly one silicone (meth)acrylate oligomer comprising on average 2 to 3 unsaturated groups. 11. The coating composition (C1a) according to any one of the preceding claims, wherein the coating composition (C1a) comprises as reactive diluent a free-radically polymerizable monomer, preferably an ethylenically-unsaturated monomer, more preferably a polyfunctional ethylenically unsaturated monomer. How to include. 12. The coating composition (C1a) according to any one of the preceding claims, wherein the coating composition (C1a) comprises hexane diol diacrylate and at least two structural units of formula (I) which may be different from each other or may be at least partially identical to each other. , preferably at least three, more preferably at least three reactive diluents selected from compounds comprising:

here
The radicals R ¹ are, independently of one another, a C ₂ -C ₈ alkylene group, very preferably a C ₂ alkylene group,
The radicals R ² are, independently of one another, H or methyl,
parameter m independently of one another is an integer in the range from 1 to 15, very preferably from 1 to 4 or from 2 to 4, provided that in at least one of the structural units of formula (I) the parameter m is at least 2, preferably exactly 2 is 12. The composition according to any one of the preceding claims, wherein the coating composition (C1a) comprises 40 to 95% by weight, preferably 50 to 85% by weight, based on the total weight of the coating composition (C1a), more preferably comprising at least one reactive diluent in a total amount of 55 to 83% by weight, preferably hexane diol diacrylate and/or (meth)acrylate derived from 6-fold ethoxylated trimethylolpropane Way. 14. The photoinitiator according to any one of claims 1 to 13, wherein the photoinitiator comprised in the coating composition (C1a) is diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl (2,4,6-trimethyl) Benzoyl)phenylphosphinate, phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide, benzophenone, 1-benzoylcyclohexan-1-ol, 2-hydroxy-2,2-dimethylacetophenone and 2,2-dimethoxy-2-phenylacetophenone and mixtures thereof. A composite (S1C1) consisting of a substrate (S1) and an at least partially embossed and at least partially cured coating (C1), wherein the coating (C1) is applied to at least a part of the surface of the substrate (S1) and is at least partially embossed It is obtainable by at least partially curing the engineered coating composition (C1a) by means of radiation curing, wherein the coating composition (C1a) is a radiation-curable coating composition comprising:
(a) from 5 to 45% by weight of at least one crosslinkable polymer and/or oligomer,
(b) 40 to 95% by weight of at least one reactive diluent;
(c) 0.01 to 15% by weight of at least one photoinitiator, and
(d) 0 to 5% by weight of at least one additive;
wherein (i) the specified total amounts of components (a), (b), (c) and (d) are each based on the total weight of the coating composition (C1a), and (ii) The total amount of all components adds up to 100% by weight;
wherein the at least one crosslinkable polymer and/or oligomer (a) comprises at least 25% by weight, preferably at least 50% by weight, based on the total weight of all crosslinkable polymers and/or oligomers comprised in the coating composition (C1a) at least one silicone (meth)acrylate oligomer in a total amount of % by weight, more preferably at least 90% by weight, very preferably 100% by weight
complex (S1C1). 16. The method according to claim 15, wherein the radiation-curable coating composition (C1a) comprises at least 50 to 95% by weight, or 50 to 85% by weight, or 50 to 83% by weight, based on the total weight of the coating composition (C1a). A complex comprising one reactive diluent (S1C1). The complex (S1C1) according to claim 15 or 16, wherein the complex (S1C1) is obtainable by carrying out the method steps (6) to (9) according to claim 9. As an embossing mold (e2) of an embossing tool (E2) for transferring the embossing structure to at least a portion of the surface of the coating composition (C2a) or to at least a portion of the surface of the coating composition (C2a) applied at least partially to the substrate (S2) Use of the complex (S1C1) according to any one of claims 15 to 17.

Images